Bendable polycarbonate resin laminate, optically transparent electromagnetic wave shield laminate, and manufacturing method thereof

ABSTRACT

The present invention provides a method for manufacturing a laminate, comprising the steps of laminating two or more layers of polycarbonate resin film and/or sheet using a (meth)acrylate-based adhesive composition containing a (A) (meth)acrylate monomer, a (B) meth(acrylate) olygomer, an (C) acrylamide derivative, and a (D) silane compound and/or an (E) organophosphorus compound to form a laminate having a thickness of 0.1 mm to 30 mm; heating the laminate at 130° C. to 185° C. so that a temperature difference between a top surface and a bottom surface of the laminate is within 20° C.; and bending the post-heating laminate into a curved shape having a radius of curvature of 10 mm or greater.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of U.S. application Ser. No.12/736,818, which is the U.S. National Stage application ofPCT/JP2009/058630, filed May 7, 2009, which claims priority fromJapanese applications JP 2008-125726, filed May 13, 2008, and JP2008-125730, filed May 13, 2008.

TECHNICAL FIELD

A preferable embodiment of the present invention relates to a bendablepolycarbonate resin laminate having superb transparency, adhesive force,heat resistance, and humidity resistance, and a manufacturing methodthereof. In more detail, the present invention relates to amanufacturing method of a polycarbonate resin laminate, comprising thesteps of laminating polycarbonate resin substrates using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having two or more layers; heating thelaminate to a temperature of 130° C. to 185° C. (preferably 150° C. to185° C.) while a temperature difference between a top surface and abottom surface of the laminate is controlled to be within 20° C.; andbending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater. The polycarbonate resin laminateaccording to the present invention is useful for covers or housings ofindustrial devices and machines, electronic devices and the like; windowmaterials or covers of automobiles, vehicles, seacrafts, aircrafts,dwellings, hospitals, office buildings and the like; and carports, resinnoise-blocking walls, security window materials, and the like usedoutdoors.

A preferable embodiment of the present invention relates to an opticallytransparent electromagnetic wave shield laminate having superbbendability and impact resistance. In more detail, the present inventionrelates to a manufacturing method of an optically transparentelectromagnetic wave shield laminate, comprising the steps oflaminating, on one or both of surfaces of an electromagnetic wave shieldlayer, a polycarbonate substrate (protecting layer) using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having two or more layers; heating thelaminate to a temperature of 130° C. to 185° C. (preferably 150° C. to185° C.) while a temperature difference between a top surface and abottom surface of the laminate is controlled to be within 20° C.; andbending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater. The optically transparent electromagneticwave shield laminate according to the present invention is useful forcovers or housings of industrial devices and machines, electronicdevices and the like; and window materials or covers of automobiles,vehicles, seacrafts, aircrafts, dwellings, hospitals, office buildingsand the like.

BACKGROUND ART

Covers and window materials for industrial devices such as semiconductorproduction devices, flat panel display production devices and the like;covers and window materials for industrial machines such as cranes,excavators and the like; window materials for automobiles, vehicles,seacrafts and aircrafts; and window materials for dwellings, hospitalsand office buildings are conventionally formed glass. Recently,synthetic resin materials are widely used for the economic points ofview of weight, fuel efficiency, and the like. Especially, polycarbonateresin laminates having superb impact resistance, heat resistance, andtransparency are preferable. However, the above-listed products are usedoutdoors and so exposed to wind and rain or sunlight, or used under theconditions of high temperature and high humidity inside vehicles.Therefore, the polycarbonate resin laminates have problems of beingclouded or peeled off due to the deterioration of the adhesive layerthereof. The above-listed products are often required to have a certainlevel of bendability from the viewpoints of design and safety. Thepolycarbonate resin laminates need to be bent at high temperaturebecause of the high heat resistance thereof, and therefore, haveproblems of being warped, air-bubbled, whitened, peeled off or the like.

As an adhesive for a polycarbonate resin laminate, Patent Document 1describes visible light-curable adhesives. A usual visible light-curableadhesive does not have a sufficient adhesive force, and so there areproblems that the polycarbonate resin laminate is peeled off when beingbent at high temperature, and also is air-bubbled or whitened due to thedeterioration or decomposition of the adhesive layer. Under theconditions of high temperature and high humidity of outdoors or insideof a vehicle, there are problems that the polycarbonate resin laminateis clouded or peeled off. For example, the visible-light curableadhesive described in the examples of Patent Document 1 (BENEFIX PCproduced by Adell Corporation) was clouded under the conditions of hightemperature and high humidity (65° C.-95% RH-24 h).

As an adhesive for a polycarbonate resin laminate, Patent Document 2describes moisture-curable hotmelt-type adhesives, thermoplasticpolyester resin adhesives, and thermoplastic silane-denatured resinadhesives. However, all of these adhesives do not have a sufficientadhesive force when being heated at a temperature of 130° or higher andso have problems that the polycarbonate resin laminate is peeled offwhen being bent at high temperature and also is air-bubbled or whiteneddue to the deterioration or decomposition of the adhesive layer. Underthe conditions of high temperature and high humidity of outdoors orinside of a vehicle, there are problems that the polycarbonate resinlaminate is clouded or peeled off.

As an adhesive for a polycarbonate resin laminate and an acrylic-basedresin laminate, Patent Document 3 describes polyurethane-based adhesivefilms. With such a polyurethane-based adhesive film, although a certainlevel of adhesive force is obtained, the polycarbonate resin laminate orthe acrylic-based resin laminate is whitened at a bent portion and thevisibility is significantly decreased. Under the conditions of hightemperature and high humidity of outdoors or inside of a vehicle, thereare problems that the polycarbonate resin laminate or the acrylic-basedresin laminate is clouded or peeled off.

Meanwhile, recently, there is a serious problem that an electromagneticwave generated from electronic devices such as personal computers,mobile phones, flat panel displays represented by liquid crystaldisplays and plasma displays, touch panels, car navigation systems,mobile information terminals and the like, motors of industrialmachines, and the like causes malfunctions of the industrial machinesand the electronic devices or communication failures. Moreover, theelectromagnetic wave is indicated as possibly having an adverseinfluence on human bodies. In order to prevent the so-calledelectromagnetic interference (hereinafter, referred to as the “EMI”),measures are now taken using various electromagnetic wave shieldmaterials.

Since a single electromagnetic wave shield material does not provide asufficient strength, electromagnetic wave shield materials are laminatedusing any of various optically transparent resin substrates or glasssubstrates. From the viewpoint of safety, an optically transparentelectromagnetic wave shield laminate using, as a substrate, apolycarbonate resin having superb impact resistance and heat resistanceis preferable. When being used for covers or housings of industrialdevices such as semiconductor production devices and the like,industrial machines, various electronic devices and the like, or forwindow materials or covers of automobiles, vehicles, seacrafts,aircrafts, dwellings, hospitals, office buildings and the like, theoptically transparent electromagnetic wave shield laminate is oftenrequired to have a certain level of bendability from the viewpoints ofdesign and safety. A polycarbonate resin needs to be bent at hightemperature because of the high heat resistance thereof, and therefore,there are problems that an optically transparent electromagnetic waveshield laminate formed of a polycarbonate resin is warped, air-bubbled,whitened, peeled off or the like. Therefore, no technology for bendingthe optically transparent electromagnetic wave shield laminate has beendisclosed.

As an adhesive for an optically transparent electromagnetic wave shieldlaminate, Patent Documents 4 and 5 describe acrylic-based, rubber-based,silicone-based, polyurethane-based, and polyester-based transparenttacky agents. Since a tacky agent does not have a sufficient adhesiveforce, there are problems that the optically transparent electromagneticwave shield laminate is peeled off when being bent at high temperatureand also air-bubbled or whitened due to the deterioration ordecomposition of the adhesive layer.

As an adhesive for an optically transparent electromagnetic wave shieldlaminate, Patent Documents 6 and 7 describe adhesive compositionscontaining, as a main component, ethylene-vinyl acetate (EVA) copolymeradhesive composition or a copolymer of ethylene, vinyl acetate and/or(meth)acrylate-based monomer. All of these materials cause faults ofbeing air-bubbled, whitened or peeled off when being bent at hightemperature due to the deterioration or decomposition of the adhesivelayer.

As an adhesive for an optically transparent electromagnetic wave shieldlaminate, Patent Document 8 describes hotmelt-type adhesives of anethylene-vinyl acetate (EVA) copolymer or an ethylene-acrylic acid estercopolymer. All of these materials have problems of being air-bubbled,whitened or peeled off when being bent at high temperature due to thedeterioration or decomposition of the adhesive layer.

As an adhesive for an optically transparent electromagnetic wave shieldlaminate, Patent Document 9 describes urethane-based adhesives. Withsuch a polyurethane-based adhesive, although a certain level of adhesiveforce is obtained, the optically transparent electromagnetic wave shieldlaminate is whitened at a bent portion and the visibility issignificantly decreased. This document discloses no explanation orexample regarding the detailed compositions of the adhesives orprocessability thereof.

Patent Document 1: Japanese Laid-Open Patent Publication No. H08-39746

Patent Document 2: Japanese Patent No. 3994404

Patent Document 3: Japanese Laid-Open Patent Publication No. H09-239936

Patent Document 4: Japanese Laid-Open Patent Publication No. 2006-319251

Patent Document 5: Japanese Laid-Open Patent Publication No. H10-163673

Patent Document 6: Japanese Laid-Open Patent Publication No. 2001-26758

Patent Document 7: Japanese Laid-Open Patent Publication No. 2001-19925

Patent Document 8: Japanese Laid-Open Patent Publication No. 2004-140283

Patent Document 9: Japanese Laid-Open Patent Publication No. H11-330778

DISCLOSURE OF THE INVENTION

The present invention has an object of providing a polycarbonate resinlaminate solving at least one of the above-described problems of theconventional art. The present invention also has an object of providinga polycarbonate resin laminate having superb transparency, adhesiveforce, heat resistance, humidity resistance, and bendability, which isnot air-bubbled, whitened or peeled off due to the deterioration ordecomposition of the adhesive layer even when being bent at hightemperature and is usable even under stringent conditions of outdoors orinside of a vehicle.

The present invention has an object of providing an opticallytransparent electromagnetic wave shield laminate solving at least one ofthe above-described problems of the conventional art. The presentinvention also has an object of providing an optically transparentelectromagnetic wave shield laminate having a superb bendability, whichis not air-bubbled, whitened or peeled off due to the deterioration ordecomposition of the adhesive layer even when being bent at hightemperature.

As a result of performing active studies in order to solve theabove-described problems, the present inventors found that at least oneof the problems can be solved by a manufacturing method of apolycarbonate resin laminate, comprising the steps of laminating two ormore layers of polycarbonate resin film and/or sheet using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a polycarbonate resin laminate; heating the laminate toa temperature of 130° C. to 185° C. (preferably 150° C. to 185° C.)while a temperature difference between a top surface and a bottomsurface of the laminate is controlled to be within 20° C.; and bendingthe post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater. A preferable embodiment of the presentinvention can provide a polycarbonate resin laminate having superbtransparency, adhesive force, heat resistance, humidity resistance, andbendability, which does not cause an adhesive layer to be air-bubbled,whitened or peeled off due to the deterioration or decomposition of theadhesive layer, or is not warped, and is usable even under stringentconditions of outdoors or inside of a vehicle.

As a result of performing active studies in order to solve theabove-described problems, the present inventors found that at least oneof the problems can be solved by a manufacturing method of an opticallytransparent electromagnetic wave shield laminate, comprising the stepsof laminating, on one or both of surfaces of an electromagnetic waveshield layer, a polycarbonate substrate (protecting layer) using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having two or more layers; heating thelaminate to a temperature of 130° C. to 185° C. (preferably 150° C. to185° C.) while a temperature difference between a top surface and abottom surface of the laminate is controlled to be within 20° C.; andbending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater. A preferable embodiment of the presentinvention can provide an optically transparent electromagnetic waveshield laminate having superb bendability, which does not cause anadhesive layer to be air-bubbled, whitened or peeled off due to thedeterioration or decomposition of the adhesive layer, or is not warped.

A method for manufacturing a polycarbonate resin laminate, amanufacturing method of an optically transparent electromagnetic waveshield laminate, and a polycarbonate resin laminate and an opticallytransparent electromagnetic wave shield laminate each obtained by therespective method, according to the present invention, encompass thefollowing embodiments.

(1) A method for manufacturing a laminate, comprising the steps of:

laminating two or more layers of polycarbonate resin film and/or sheetusing a (meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having a thickness of 0.1 mm to 30 mm;

heating the laminate at 130° C. to 185° C. so that a temperaturedifference between a top surface and a bottom surface of the laminate iswithin 20° C.; and

bending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater.

(2) The method for manufacturing a laminate according to (1) above,wherein the step of heating the laminate is the step of heating thelaminate at 150° C. to 185° C.

(3) The method for manufacturing a laminate according to (1) or (2)above, wherein one of the two or more layers of polycarbonate resin filmand/or sheet is an electromagnetic wave shield layer, and at least oneof the two or more layers is a protecting layer.

(4) The method for manufacturing a laminate according to (3) above,wherein the electromagnetic wave shield layer contains a conductivecompound containing at least one metal component selected from the groupconsisting of silver, copper, aluminum, nickel, carbon, ITO (indiumoxide/tin oxide), ZnO, tin, zinc, titanium, tungsten and stainlesssteel.

(5) The method for manufacturing a laminate according to (3) or (4)above, wherein the electromagnetic wave shield layer has anelectromagnetic wave shield performance of 30 decibel or greater.

(6) The method for manufacturing a laminate according to any one of (3)through (5) above, wherein the electromagnetic wave shield layercontains at least one selected from the group consisting of a metal thinfilm mesh, a metal woven mesh, a conductive fiber mesh, and a conductiveprinted mesh.

(7) The method for manufacturing a laminate according to (6) above,wherein the metal thin film mesh and the conductive printed mesh have abase substrate containing a polycarbonate resin, a polyethyleneterephthalate resin, or a polyester resin.

(8) The method for manufacturing a laminate according to any one of (1)through (7) above, wherein the laminate has a 180 degree peel strengthof 50 N/25 mm width or greater.

(9) The method for manufacturing a laminate according to any one of (1)through (8) above, wherein the laminate is not peeled or clouded afterbeing treated for 200 hours under conditions of 65° C. and 95 RH %.

(10) The method for manufacturing a laminate according to any one of (1)through (9) above, wherein the (B) (meth)acrylate oligomer is at leastone (meth)acrylate oligomer selected from the group consisting ofurethane(meth)acrylate oligomer, polyester(meth)acrylate oligomer,epoxy(meth)acrylate oligomer, and polyol(meth)acrylate oligomer.

(11) The method for manufacturing a laminate according to (10) above,wherein the urethane(meth)acrylate oligomer is an alicyclic hydrocarboncompound.

(12) The method for manufacturing a laminate according to (11) above,wherein the urethane(meth)acrylate oligomer, which is the alicyclichydrocarbon compound, is a compound derived fromdicyclohexylmethaneisocyanate.

(13) The method for manufacturing a laminate according to any one of (1)through (12) above, wherein the (C) acrylamide derivative is alkylacrylamide and/or alkyl methacrylamide.

(14) The method for manufacturing a laminate according to any one of (1)through (13) above, wherein the (C) acrylamide derivative is at leastone selected from the group consisting of dimethyl acrylamide, isopropylacrylamide, diethyl acrylamide, and 4-acrylomorpholine.

(15) The method for manufacturing a laminate according to any one of (1)through (14) above, wherein the (D) silane compound is at least oneselected from the group consisting of amino-functional silane,epoxy-functional silane, vinyl-functional silane, mercapto-functionalsilane, methacrylate-functional silane, acrylamide-functional silane,and acrylate-functional silane.

(16) The method for manufacturing a laminate according to any one of (1)through (15) above, wherein the (D) silane compound is(3-(2,3-epoxypropoxy)propyl)trimethoxysilane.

(17) The method for manufacturing a laminate according to any one of (1)through (16) above, wherein the (E) organophosphorus compound is anacrylate phosphate compound.

(18) The method for manufacturing a laminate according to any one of (1)through (17) above, wherein the meth(acrylate)-based adhesivecomposition is a non-solvent (meth)acrylate-based adhesive composition.

(19) The method for manufacturing a laminate according to any one of (1)through (18) above, wherein the (meth)acrylate-based adhesivecomposition is a photocurable (meth)acrylate-based adhesive compositionwhich is curable by visible light, an ultraviolet ray (UV) or anelectron beam (EB).

(20) The method for manufacturing a laminate according to any one of (1)through (19) above, comprising the step of forming a cover filmcontaining at least one selected from the group consisting of anantioxidant, an ultraviolet absorber and a photostabilizer on one orboth of the surfaces of the laminate.

(21) The method for manufacturing a laminate according to (20) above,wherein the cover film contains a thermosetting resin or a photocurableresin.

(22) The method for manufacturing a laminate according to (20) or (21)above, wherein the cover film contains an acrylic-based resin compoundor a silicone-based resin compound.

(23) The method for manufacturing a laminate according to any one of (1)through (22) above, wherein the layers containing the polycarbonateresin or the layers containing the (meth)acrylate-based adhesivecomposition contain at least one selected from the group consisting ofan antioxidant, an ultraviolet absorber and a photostabilizer.

(24) A laminate manufactured by the method of any one of (1) through(23) above.

(25) The laminate of (24) above, which is usable for a cover of anelectronic device, a shield material for a housing, a cover for avehicle, a cover for a semiconductor production devices, or a shieldmaterial for a window material.

(26) A method for manufacturing a polycarbonate resin laminate,comprising the steps of:

laminating two or more layers of polycarbonate resin film and/or sheetusing a (meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a polycarbonate resin laminate having a thickness of0.1 mm to 30 mm;

heating the laminate at 130° C. to 185° C. (preferably 150° C. to 185°C.) so that a temperature difference between a top surface and a bottomsurface of the laminate is within 20° C.; and

bending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater.

(27) A method for manufacturing an optically transparent electromagneticwave shield laminate, comprising the steps of:

laminating, on one or both of surfaces of an electromagnetic wave shieldlayer, a polycarbonate substrate (protecting layer) using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having a thickness of 0.1 mm to 30 mm;

heating the laminate at 130° C. to 185° C. (preferably 150° C. to 185°C.) so that a temperature difference between a top surface and a bottomsurface of the laminate is within 20° C.; and

bending the post-heating laminate into a curved shape having a radius ofcurvature of 10 mm or greater.

A polycarbonate resin laminate according to a preferable embodiment ofthe present invention does not cause an adhesive layer to beair-bubbled, whitened or peeled off due to the deterioration ordecomposition of the adhesive layer, or is not warped, even when beingbent at high temperature and is usable even under stringent conditionsof outdoors or inside of a vehicle. Therefore, such a polycarbonateresin laminate is usable for a wide range of covers and window materialswhich need to have superb transparency, durability and bendability atthe same time. Such covers and window materials include covers andwindow materials for industrial devices such as semiconductor productiondevices, flat panel display production devices and the like; covers andwindow materials for industrial machines such as cranes, excavators andthe like; window materials for automobiles, vehicles, seacrafts andaircrafts; and window materials for dwellings, hospitals and officebuildings; which need to have superb transparency, adhesive force, heatresistance, humidity resistance, and bendability.

An optically transparent electromagnetic wave shield laminate accordingto a preferable embodiment of the present invention does not cause anadhesive layer to be air-bubbled, whitened or peeled off due to thedeterioration or decomposition of the adhesive layer, or is not warped,even when being bent at high temperature. Therefore, such an opticallytransparent electromagnetic wave shield laminate is usable for a widerange of electromagnetic wave shields which need to have superbelectromagnetic wave shield performance, transparency, visibility, andbendability at the same time. Such electromagnetic wave shields includecovers and housings of industrial devices and machines, electronicdevices and the like, and window materials and covers of automobiles,vehicles, seacrafts, aircrafts, dwellings, hospitals and officebuildings, which need to have superb transparency, visibility, andbendability.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, a manufacturing method of a polycarbonate resin laminate, amanufacturing method of an optically transparent electromagnetic waveshield laminate, and a polycarbonate resin laminate and an opticallytransparent electromagnetic wave shield laminate each obtained by therespective method, according to the present invention, will be describedin detail.

A manufacturing method of a polycarbonate resin laminate according tothe present invention comprises the steps of laminating two or morelayers of polycarbonate resin film and/or sheet using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a polycarbonate resin laminate having a thickness of0.1 mm to 30 mm; heating the laminate to a temperature of 130° C. to185° C. (preferably 150° C. to 185° C.) while a temperature differencebetween a top surface and a bottom surface of the laminate is controlledto be within 20° C.; and bending the post-heating laminate into a curvedshape having a radius of curvature of 10 mm or greater.

A manufacturing method of an optically transparent electromagnetic waveshield laminate according to the present invention comprises the stepsof laminating, on one or both of surfaces of an electromagnetic waveshield layer, a polycarbonate substrate (protecting layer) using a(meth)acrylate-based adhesive composition containing a (A)(meth)acrylate monomer, a (B) meth(acrylate) oligomer, an (C) acrylamidederivative, and a (D) silane compound and/or an (E) organophosphoruscompound to form a laminate having two or more layers, the laminatehaving a thickness of 0.1 mm to 30 mm; heating the laminate to atemperature of 130° C. to 185° C. (preferably 150° C. to 185° C.) whilea temperature difference between a top surface and a bottom surface ofthe laminate is controlled to be within 20° C.; and bending thepost-heating laminate into a curved shape having a radius of curvatureof 10 mm or greater.

A polycarbonate resin laminate and an optically transparentelectromagnetic wave shield laminate manufactured by the respectivemanufacturing methods according to the present invention each have a 180degree peel strength of preferably 50 N/25 mm width or greater and morepreferably 50 to 300 N/25 mm width. A 180 degree peel strength of 50N/25 mm width or greater is preferable because the laminate is notpeeled off when being bent or bored.

The optically transparent electromagnetic wave shield laminate accordingto the present invention has two or more layers which include anelectromagnetic wave shield layer, for preventing influx of anelectromagnetic wave generated from various electronic devices,machines, motors and the like, and a polycarbonate substrate (protectinglayer). The protecting layer may be provided on one or both of surfacesof the electromagnetic wave shield layer from the viewpoints of impactresistance, scratch resistance, weather resistance, water resistance,antistatic property, humidity resistance, antifogging property,anti-reflection property, contamination resistance and the like. Thepresent invention encompasses all the laminate types of opticallytransparent electromagnetic wave shield laminate including anelectromagnetic wave shield layer formed of a metal thin film mesh, ametal woven mesh, a conductive fiber mesh or a conductive printed meshusing a conductive compound.

The electromagnetic wave shield performance of the electromagnetic waveshield layer is preferably 30 decibel or greater. When theelectromagnetic wave shield performance is less than 30 decibel, theelectromagnetic wave shield layer cannot prevent influx of theelectromagnetic wave generated from an electronic device completely andso may possibly cause malfunctions or communication failures of othermachines or electronic devices, and cannot prevent invasion of theelectromagnetic wave from the outside of the electronic device and maypossibly damage the electronic device.

In order to realize the above-mentioned electromagnetic wave shieldperformance, the surface resistance ratio (sheet resistance value) ofthe electromagnetic wave shield layer is preferably 10[Ω/□] or less.More preferably, the surface resistance ratio is 1[Ω/□] or less, andstill more preferably 0.1[Ω/□] or less.

For forming the electromagnetic wave shield layer, any conductivecompound is usable with no specific limitation. For example, a metalcompound containing at least one metal component selected from iron,gold, silver, copper, aluminum, nickel, carbon, ITO (indium oxide/tinoxide), ZnO (zinc oxide), tin, zinc, titanium, tungsten and stainlesssteel is usable. From an economic point of view, it is preferable to usea metal compound containing at least one metal component selected fromsilver, copper, aluminum, nickel, carbon, ZnO (zinc oxide), tin, andstainless steel.

The electromagnetic wave shield layer may contain, for example, a metalthin film mesh, a metal woven mesh, a conductive fiber mesh, or aconductive printed mesh each using a conductive compound. There is nospecific limitation on the method for producing a metal thin film mesh.Usable methods include, for example, a method of forming a metal thinfilm of copper, silver, aluminum, ITO (indium oxide/tin oxide), ZnO(zinc oxide) or the like on a surface of an optically transparentorganic polymer material film or sheet by vapor deposition orsputtering; a method of bonding foils of such a metal with an adhesive,and then forming a mesh by etching or the like; a method of applying aplating catalyst-containing ink or paste by gravure printing, inkjetprinting, screen printing or the like, and then forming a mesh byelectroless plating or electric plating; a method of rolling a metalplate of copper, silver, aluminum or the like to form a metal foilhaving a predetermined thickness and punching the metal foil to form amesh; and the like. Such a metal thin film mesh is preferably blackenedon one or both of surfaces thereof from the viewpoints of waterresistance, humidity resistance, corrosion resistance, rust resistance,and anti-reflection property. The metal thin film mesh preferably has aline width in the range of 5 to 200 μm, a thickness in the range of 0.01to 100 μm, and a pitch in the range of 100 to 1000 μm from theviewpoints of electromagnetic wave shield performance and transparency.

As an adhesive for metal foil usable for forming the metal thin filmmesh, any known adhesive or tacky agent having good transparency, waterresistance, humidity resistance and adhesive force is usable with nospecific limitation. Examples of the adhesive include known photocurableadhesive, thermosetting adhesive, hotmelt-type adhesive and the like.

Examples of the tacky agent include known acrylic-based resincomposition, polyurethane-based resin composition, polyester-based resincomposition, epoxy-based resin composition, silicone-based resincomposition, rubber-based resin composition, and the like. Among these,acrylic-based resin composition, which has good transparency, waterresistance, humidity resistance and adhesive force, is most preferableas the tacky agent.

Examples of the hotmelt-type adhesive include polyolefin-based resincomposition such as ethylene-(meth)acrylic acid copolymer resincomposition, ethylene-(meth)acrylic acid ester copolymer resincomposition or the like; polystyrene-based resin composition; ethylenevinyl acetate-based resin composition; vinyl acetate-based resincomposition; acrylic-based resin composition; polyurethane-based resincomposition; polyester-based resin composition; epoxy-based resincomposition; polyester-based resin composition; polyamide-based resincomposition; polyvinylether-based resin composition; silicone-basedresin composition; rubber-based resin composition; and the like. Amongthese, acrylic-based resin composition, which has good transparency,water resistance, humidity resistance and adhesive force, is mostpreferable as the hotmelt-type adhesive.

There is no specific limitation on the thermosetting adhesive as long asthe adhesive is polymerizable by heat. Examples of the thermosettingadhesive include compounds having a functional group such as glycidylgroup, acryloyl group, methacryloyl group, hydroxyl group, carboxylgroup, isocyanurate group, amino group, amide group or the like. Thesecompounds are usable independently or in a combination of two or more.Usable compounds include, for example, epoxy-based resin composition,acrylic-based resin composition, silicone-based resin composition,phenol-based resin composition, thermosetting polyimide-based resincomposition, polyurethane-based resin composition, polyester-based resincomposition, melamine-based resin composition, urea-based resincomposition and the like. From the viewpoints of adhesive force andtransparency, acrylate-based resin compositions such as epoxyacrylate-based resin composition, urethane acrylate-based resincomposition, polylether acrylate-based resin composition, polyesteracrylate-based resin composition, and the like are preferable.Optionally, two or more of these thermosetting adhesives are usabletogether. Together with a thermosetting adhesive composition, a curingagent is preferably used. Usable curing agents include known curingagents such as isocyanate-based curing agent; amines such astriethylenetetramine, xylenediamine, N-aminotetramine,diaminodiphenylmethane and the like; acid anhydrides such as phthalicanhydride, maleic anhydride, dodecylsuccinic anhydride, pyromelliticanhydride, benzophenonetetracarboxylic anhydride, and the like;diaminodiphenylsulfone; tris(dimethylaminomethyl)phenol, polyamideresin, dicyandiamide; ethylmethylimidazole; and the like. These curingagents are usable independently or in a combination of two or more.

The photocurable adhesive is preferably at least one(meth)acrylate-based adhesive composition selected from, for example,urethane(meth)acrylate-based adhesive composition,polyester(meth)acrylate-based adhesive composition,epoxy(meth)acrylate-based adhesive composition, andpolyol(meth)acrylate-based adhesive composition. Among these,urethane(meth)acrylate-based adhesive composition is especiallypreferable from the viewpoints of water resistance, humidity resistance,weather resistance, transparency and adhesive force.

Photocurable (meth)acrylate-based adhesive composition, which is curablewhen being irradiated with an active energy beam, is especiallypreferable in terms of curing time and safety. As the active energybeam, visible light or ultraviolet is preferable.

A conductive printed mesh obtained by any production method is usablewith no specific limitation. The following method is one example. Ametal particle compound of copper, silver, aluminum, nickel or the likeor carbon is mixed with a binder of, for example, an epoxy-based,urethane-based, acrylic-based, or EVA-based resin to form an ink orpaste. Using this ink or paste, a mesh is formed on a film or sheetsurface of an optically transparent organic polymer material by screenprinting, gravure printing, offset printing or the like. The conductiveprinted mesh preferably has a line width in the range of 10 to 200 μm, athickness in the range of 1 to 100 μm, and a pitch in the range of 100to 1000 μm from the viewpoints of electromagnetic wave shieldperformance and transparency.

Examples of the optically transparent organic polymer material used forthe film or sheet substrate for forming the metal thin film mesh or theconductive printed mesh include polycarbonate resin, polyethyleneterephthalate resin, polyester resin, polyethersulfone resin,polyethylene naphthalate resin, polystyrene resin, polyurethane resin,polyvinyl alcohol resin, polymethyl methacrylate resin, alicyclicpolylolefin resin, optically transparent polyimide resin, polyamideresin, acrylic resin, polyacrylonitrile resin, polyvinyl chloride resin,polyvinylidene chloride resin, polypropylene resin, polyethylene resinand the like.

Among these optically transparent organic polymer materials,polycarbonate resin, polyester resin, and polyethylene terephthalateresin are especially preferable from the viewpoints of transparency,impact resistance, and versatility of use.

A metal fabric mesh obtained by any production method is usable with nospecific limitation. According to an example of the method, a mesh isformed by knitting metal wires of stainless steel, copper, silver, gold,iron or the like. A mesh having a smaller mesh size and a largerdiameter of the metal wires has a higher electromagnetic wave shieldperformance but has a lower visibility. Therefore, the mesh size ispreferably in the range of 50 to 300 mesh, and the diameter of the metalwires is preferably in the range of 10 to 200 μm. Herein, the mesh sizemeans the mesh size defined by the Taylor sieve.

A conductive fiber mesh obtained by any production method is usable withno specific limitation. According to an example of the method, asurface-treated synthetic fiber of polyester or the like is treated withelectroless plating using a conductive metal compound such as nickel,copper or the like, and then blackened. The mesh size is preferably inthe range of 50 to 300 mesh, and the diameter of the fiber is preferablyin the range of 10 to 100 μm.

As described above, the optically transparent electromagnetic waveshield laminate according to the present invention has a polycarbonatesubstrate (protecting layer) on one or both of surfaces of theelectromagnetic wave shield layer from the viewpoints of impactresistance, scratch resistance, weather resistance, water resistance,anti-static property, humidity resistance, antifogging property,anti-reflection property, contamination resistance and the like. Theprotecting layer may be formed of a film or sheet of an opticallytransparent organic polymer material or a cover film having any ofvarious functions as long as being formed of a material which is visibleand optically transparent (mainly formed of polycarbonate).

The polycarbonate resin laminate according to the present invention alsopreferably has a protecting layer on one or both of surfaces thereoffrom the viewpoints of impact resistance, scratch resistance, weatherresistance, water resistance, anti-static property, humidity resistance,antifogging property, anti-reflection property, contamination resistanceand the like. Herein, the protecting layer may be formed of a film orsheet of an optically transparent organic polymer material or a coverfilm having any of various functions as long as being formed of amaterial which is visible and optically transparent.

Any optically transparent organic polymer material which is visible andoptically transparent is usable with no specific limitation. The“optically transparent organic polymer material” encompasses bonded,vapor-deposited, applied, printed or processed materials, such asvarious metal compounds, conductive compounds, organic compounds,inorganic compounds and the like. Examples of the optically transparentorganic polymer material include polycarbonate resin, polyethyleneterephthalate resin, polyester resin, polyether sulfone resin,polyethylene naphthalate resin, polystyrene resin, polyurethane resin,polyvinyl alcohol resin, polymethyl methacrylate resin, alicyclicpolylolefin resin, optically transparent polyimide resin, polyamideresin, acrylic resin, polyacrylonitrile resin, polyvinyl chloride resin,polyvinylidene chloride resin, polypropylene resin, polyethylene resin,and the like.

For the cover film, any material is usable with no specific limitation.Preferable materials include silicone resin-based compound having a highdurability against long-time use and a relatively high surface hardness,and acrylic resin and polyfunctional acrylic resin, which are relativelyeasy to be treated and provide a good cover film. The method for curingsuch a cover film varies in accordance with the properties of the resincompound used. In consideration of the productivity and convenience, itis preferable to select a thermosetting or photocurable resin. Anexample of the photocurable resin is a resin composition formed of asingle or a plurality of types of resins such as mono-functional orpolyfunctional acrylate monomer, oligomer or the like, to which aphotoinitiator is added as a curing catalyst. Examples of thethermosetting resin include polyorganosiloxane-based resin, crosslinkedacrylic-based resin, and the like. Such a resin composition iscommercially available as a hard coat, and an appropriate type may beselected in consideration of the compatibility with the material of thecover film.

To such a cover film, ultraviolet absorber, photostabilizer, andantioxidant may be added, and optionally, various types of stabilizerssuch as organic solvent, anti-coloring agent and the like; levelingagent; defoaming agent; thickener; antistatic agent; surfactant such asantifogging agent and the like; etc. may be optionally added.

For the optically transparent electromagnetic wave shield laminateaccording to the present invention, it is preferable to optionallyinstall a ground wire in order to fully provide the shieldingperformance thereof and prevent a leak of the electromagnetic wave.There is no specific limitation on the method for installing the groundwire. Examples of the method are as follows. According to one method, ametal particle compound of copper, silver, aluminum, nickel or the likeor carbon is mixed with a binder of, for example, an epoxy-based,urethane-based, acrylic-based, or EVA-based resin to form a conductivepaste, and this paste is applied to an outer perimeter of an end surfaceof the optically transparent electromagnetic wave shield laminate.According to another method, an outer perimeter of an end surface of theoptically transparent electromagnetic wave shield laminate is coveredwith a conductive tape. These methods may be combined. It is preferablethat at least 70% of the outer perimeter of the end surface is coveredwith the conductive paste or tape.

The (meth)acrylate-based adhesive composition used in the presentinvention is preferably at least one selected fromurethane(meth)acrylate-based adhesive composition,polyester(meth)acrylate-based adhesive composition,epoxy(meth)acrylate-based adhesive composition, andpolyol(meth)acrylate-based adhesive composition, and more preferablyurethane(meth)acrylate-based adhesive composition.

In consideration of the environmental friendliness and ease of handling,the (meth)acrylate-based adhesive composition used in the presentinvention is preferably a solvent-free (meth)acrylate-based adhesivecomposition. Preferable examples of the solvent-free(meth)acrylate-based adhesive composition include photocurable(meth)acrylate-based adhesive composition, thermosetting(meth)acrylate-based adhesive composition, hotmelt-type(meth)acrylate-based adhesive composition, and the like. Among these,photocurable (meth)acrylate-based adhesive composition which is curablewhen being irradiated with active energy is especially preferable interms of curing time and safety. As the active energy, visible light andultraviolet are preferable.

In the present invention, any of various types of (A)(meth)acrylate-based polymerizable monomer is usable with no specificlimitation. Examples of the (meth)acrylate-based polymerizable monomerinclude mono-, di-, and poly(meth)acrylate compounds, of aliphaticalcohol, diol and polyhydric alcohol having a carbon number of 2 to 20;poly(meth)acrylate of hydroxy-terminated compound having a carbon numberof 30 or less, having an aliphatic ether bond, an ester bond or acarbonate bond branched by a polyhydric alcohol such as glycerin,trimethylol propane, pentaerythritol or the like; compound having analicyclic compound or an aromatic compound in the backbone thereof; andthe like. Specific examples thereof include mono-functional(meth)acrylate-based polymerizable monomer having one (meth)acryloyloxygroup in one molecule (hereinafter, referred to as the “mono-functional(meth)acrylate monomer”), bi-functional (meth)acrylate-basedpolymerizable monomer having two (meth)acryloyloxy groups in onemolecule (hereinafter, referred to as the “bi-functional (meth)acrylatemonomer”), and polyfunctional (meth)acrylate-based polymerizable monomerhaving at least three (meth)acryloyloxy groups in one molecule(hereinafter, referred to as the “polyfunctional (meth)acrylatemonomer”). A single type of, or a combination of two or more types of,the (meth)acrylate monomer is usable.

Specific examples of the mono-functional (meth)acrylate monomer includetetrahydrofurfuryl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate,2-hydroxy-3-phenoxypropyl(meth)acrylate, isobutyl(meth)acrylate,t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,cyclohexyl(meth)acrylate, dicyclopentenyl(meth)acrylate,benzyl(meth)acrylate, isobornyl(meth)acrylate,phenoxyethyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, ethylcarbitol(meth)acrylate,trimethylolpropane mono(meth)acrylate, pentaerythritolmono(meth)acrylate, and phenoxypolyethyleneglycol(meth)acrylate. Inaddition, examples of carboxyl group-containing (meth)acrylate monomerinclude 2-(meth)acryloyloxyethylphthalic acid,2-(meth)acryloyloxyethylhexahydrophthalic acid,carboxyethyl(meth)acrylate, 2-(meth)acryloyloxyethylsuccinic acid,N-(meth)acryloyloxy-N′,N′-dicarboxy-p-phenylenediamine,4-(meth)acryloyloxyethyltrimellitic acid, and the like. The“mono-functional (meth)acrylate monomer” encompasses vinyl-containingmonomers such as N-vinylpyrrolidone and the like, and(meth)acryloylamino group-containing monomers such as4-(meth)acryloylamino-1-carboxymethylpiperidine and the like.

Representative examples of the bi-functional (meth)acrylate monomerinclude alkyleneglycol di(meth)acrylates, polyoxyalkyleneglycoldi(meth)acrylates, halogen-substituted alkyleneglycol di(meth)acrylates,di(meth)acrylate of fatty acid polyol, alkylene oxide-adductdi(meth)acrylates of bisphenol A or bisphenol F, epoxy di(meth)acrylatesof bisphenol A or bisphenol F, and the like. The bi-functional(meth)acrylate monomer is not limited to these, and various othermaterials are usable. Specific examples of the bi-functional(meth)acrylate monomer include ethyleneglycol di(meth)acrylate,1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate,neopentylglycol di(meth)acrylate, trimethylolpropane di(meth)acrylate,pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate,diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate,dipropyleneglycol di(meth)acrylate, tripropyleneglycol di(meth)acrylate,polyethyleneglycol di(meth)acrylate, polypropyleneglycoldi(meth)acrylate, polytetramethyleneglycol di(meth)acrylate,hydroxypivalic acid ester neopentylglycol di(meth)acrylate,2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane,2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane,2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]methane, water-added dicyclop entadienyl di(meth)acrylate, and tris(hydroxyethyl)isocyanuratedi(meth)acrylates.

Representative examples of the polyfunctional (meth)acrylate monomerinclude poly(meth)acrylates of at least trihydric aliphatic polyol suchas glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate,ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, and the like. Other examples of thepoly(meth)acrylate monomer include poly(meth)acrylates of at leasttrihydric halogen-substituted polyol, glycerin alkylene oxide-adducttri(meth)acrylate, trimethylolpropane alkylene oxide-adducttri(meth)acrylate, 1,1,1-tris[(meth)acryloyloxyethoxyethoxy]propane, andtris(hydroxyethyl)isocyanurate tri(meth)acrylates.

Examples of the (B) (meth)acrylate oligomer used in the presentinvention include at least bi-functional polyfunctionalurethane(meth)acrylate oligomer (hereinafter, referred to as the“polyfunctional urethane(meth)acrylate oligomer”), at leastbi-functional polyfunctional polyester(meth)acrylate oligomer(hereinafter, referred to as the “polyfunctional polyester(meth)acrylateoligomer”), at least bi-functional polyfunctional epoxy(meth)acrylateoligomer (hereinafter, referred to as the “polyfunctionalepoxy(meth)acrylate oligomer”), at least bi-functional polyfunctionalpolyol(meth)acrylate oligomer (hereinafter, referred to as the“polyfunctional polyol(meth)acrylate oligomer”), and the like. A singletype of, or a combination of two or more types of, the (meth)acrylateoligomer is usable.

An example of the polyfunctional urethane(meth)acrylate oligomer is aurethanization reaction product of an isocyanate compound obtained byreacting a polyol with polyisocyanate and a (meth)acrylate monomerhaving at least one (meth)acryloyloxy group and at least one hydroxylgroup in one molecule. Among the urethane(meth)acrylate-based oligomers,urethane(meth)acrylate-based oligomers containing an alicyclichydrocarbon compound, which is superb in water resistance, humidityresistance, weather resistance, and adhesive force, are preferable.Among these, a urethane(meth)acrylate-based oligomer using isophoronediisocyanate or dicyclohexylmethane diisocyanate as a starting materialis more preferable. A urethane(meth)acrylate-based oligomer usingdicyclohexylmethane diisocyanate as a starting material is especiallypreferable.

Examples of the (meth)acrylate monomer having at least one(meth)acryloyloxy group and at least one hydroxyl group in one moleculeand used for the urethanization reaction include2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate,glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, andpentaerythritol tri(meth)acrylate, and dipentaerythritolpenta(meth)acrylate.

Examples of the polyisocyanate used for the urethanization reactioninclude di- or tri-isocyanate such as hexamethylene diisocyanate, lysinediisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate,tolylene diisocyanate, xylylene diisocyanate, diisocyanate (among thesediisocyanates) obtained by adding hydrogen to aromatic isocyanate (e.g.,diisocyanate such as hydrogen-added tolylene diisocyanate,hydrogen-added xylylene diisocyanate, or the like), triphenylmethanetriisocyanate, dimethylenetriphenyl triisocyanate and the like; andpolyisocyanate obtained by multimerization of diisocyanate. Among these,isophorone diisocyanate and dicyclohexylmethane diisocyanate, which aresuperb in water resistance, humidity resistance, and weather resistance,are preferable. Dicyclohexylmethane diisocyanate is especiallypreferable.

Example of the polyol generally used for the urethanization reactioninclude aromatic, aliphatic and alicyclic polyols, and also polyesterpolyol, polyether polyol, and the like. Usually, examples of thealiphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol,neopentylglycol, ethyleneglycol, propyleneglycol, trimethylolethane,trimethylolpropane, dimethylolheptane, dimethylolpropionic acid,dimethylolbutylionic acid, glycerin, water-added bisphenol A, and thelike.

Polyester polyol is obtained by dehydrogenation-condensation reaction ofa polyol described above and a polybasic carboxylic acid (anhydride).Specific examples of the polybasic carboxylic acid include succinic acid(anhydride), adipic acid, maleic acid (anhydride), trimellitic acid(anhydride), hexahydrophthalic acid (anhydride), phthalic acid(anhydride), isophthalic acid, terephthalic acid, and the like. Examplesof the polyether polyol include polyalkyleneglycol, andpolyoxyalkylene-denatured polyol obtained by the reaction of a polyol orphenol with alkylene oxide.

As the urethane(meth)acrylate-based oligomer, many types arecommercially available and easily obtainable. Examples of theurethane(meth)acrylate-based oligomer include Beam Set 575, Beam Set551B, Beam Set 550B, Beam Set 505A-6, Beam Set 504H, Beam Set 510, BeamSet 502H, Beam Set 575CB, and Beam Set 102 (trade names of theurethane(meth)acrylate-based oligomers produced by Arakawa ChemicalIndustries, Ltd.); Photomer 6008 and Photomer 6210 (trade names of theurethane(meth)acrylate-based oligomers produced by San Nopco Limited);NK Oligo U-4HA, NK Oligo U-108A, NK Oligo U-1084A, NK Oligo U-200AX, NKOligo U-122A, NK Oligo U-340A, NK Oligo U-324A, NK Oligo UA-100, and NKOligo MA-6 (trade names of the urethane(meth)acrylate-based oligomersproduced by Shin-Nakamura Chemical Co., Ltd.); Aronix M-1100, AronixM-1200, Aronix M-1210, Aronix M-1310, Aronix M-1600, and Aronix M-1960(trade names of the urethane(meth)acrylate-based oligomers produced byToagosei Co., Ltd.); AH-600, AT-606, and UA-306H (trade names of theurethane(meth)acrylate-based oligomers produced by Kyoeisha ChemicalCo., Ltd.); Karayad UX-2201, Karayad UX-2301, Karayad UX-3204, KarayadUX-3301, Karayad UX-4101, Karayad UX-6101, and Karayad UX-7101 (tradenames of the urethane(meth)acrylate-based oligomers produced by NipponKayaku Co., Ltd.); Shiko UV-1700B, Shiko UV-3000B, Shiko UV-3300B, ShikoUV-3520TL, Shiko UV-3510TL, Shiko UV-6100B, Shiko UV-6300B, ShikoUV-7000B, Shiko UV-7210B, Shiko UV-7550B, Shiko UV-2000B, ShikoUV-2250TL, Shiko UV-2010B, Shiko UV-2580B, and Shiko UV-2700B (tradenames of the urethane(meth)acrylate-based oligomers produced by TheNippon Synthetic Chemical Industry Co., Ltd.); Artresin UN-9000PEP,Artresin UN-9200A, Artresin UN-9000H, Artresin UN-1255, ArtresinUN-5200, Artresin UN-2111A, Artresin UN-330, Artresin UN-3320HA,Artresin UN-3320HB, Artresin UN-3320HC, Artresin UN-3320HS, and ArtresinUN-6060P (trade names of the urethane(meth)acrylate-based oligomersproduced by Negami Chemical Industrial Co., Ltd.); Laromer UA19T,Laromer LR8949, Laromer LR8987, and Laromer LR8983 (trade names of theurethane(meth)acrylate-based oligomers produced by BASF); DiabeamUK6053, Diabeam UK6055, Diabeam UK6039, Diabeam UK6038, Diabeam UK6501,Diabeam UK6074, and Diabeam UK6097 (trade names of theurethane(meth)acrylate-based oligomers produced by Mitsubishi Rayon Co.,Ltd.); Ebecryl 254, Ebecryl 264, Ebecryl 265, Ebecryl 1259, Ebecryl4866, Ebecryl 1290K, Ebecryl 5129, Ebecryl 4833, and Ebecryl 2220 (tradenames of the urethane(meth)acrylate-based oligomers produced by DaicelUCB Kabushik Kaisha); and the like.

The polyfunctional polyester(meth)acrylate oligomer is obtained bydehydrogenation-condensation reaction of a (meth)acrylic acid, apolybasic carboxylic acid (anhydride) and a polyol. Examples of thepolybasic carboxylic acid (anhydride) used for thedehydrogenation-condensation reaction include succinic acid (anhydride),adipic acid, maleic acid (anhydride), itaconic acid (anhydride),trimellitic acid (anhydride), pyromellitic acid (anhydride),hexahydrophthalic acid (anhydride), phthalic acid (anhydride),isophthalic acid, terephthalic acid, and the like. Examples of thepolyol used for the dehydrogenation-condensation reaction include1,4-butanediol, 1,6-hexanediol, diethyleneglycol, triethyleneglycol,propyleneglycol, neopentylglycol, dimethylolheptane, dimethylolpropionicacid, dimethylolbutylionic acid, trimethylolpropane,ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

Specific examples of the polyester(meth)acrylate-based oligomer includeAronix M-6100, Aronix M-7100, Aronix M-8030, Aronix M-8060, AronixM-8530, and Aronix M-8050 (trade names of thepolyester(meth)acrylate-based oligomers produced by Toagosei Co., Ltd.);Laromer PE44F, Laromer LR8907, Laromer PE55F, Laromer PE46T, and LaromerLR8800 (trade names of the polyester(meth)acrylate-based oligomersproduced by BASF); Ebecryl 80, Ebecryl 657, Ebecryl 800, Ebecryl 450,Ebecryl 1830, and Ebecryl 584 (trade names of thepolyester(meth)acrylate-based oligomers produced by Daicel UCB KabushikKaisha); Photomer RCC13-429 and Photomer 5018 (trade names of thepolyester(meth)acrylate-based oligomers produced by San Nopco Limited);and the like.

The polyfunctional epoxy(meth)acrylate oligomer is obtained by additionreaction of a polyglycidylether and a (meth)acrylic acid. Any of varioustypes of epoxy(meth)acrylate-based oligomer is usable with no specificlimitation. The epoxy(meth)acrylate-based oligomer has a structureobtained by adding an epoxy-based oligomer and a (meth)acrylic acid, andis available in bisphenol A-epichlorhydrin-type, denatured bisphenolA-type, amine-denatured-type, phenolnovolac-epichlorhydrin-type,aliphatic type, alicyclic type and the like. Examples of thepolyglycidylether include ethyleneglycoldiglycidylether,propyleneglycoldiglycidylether, tripropyleneglycoldiglycidylether,1,6-hexanedioldiglycidylether, bisphenol A diglycidylether, and thelike.

Specific examples of the epoxy(meth)acrylate-based oligomer includeLaromer LR8986, Laromer LR8713, and Laromer EA81 (trade names of theepoxy(meth)acrylate-based oligomers produced by BASF); NK Oligo EA-6310,NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6320, NK Oligo EA-7440,and NK Oligo EA-6340 (trade names of the epoxy(meth)acrylate-basedoligomers produced by Shin-Nakamura Chemical Co., Ltd.); Ebecryl 3700,Ebecryl 3200, and Ebecryl 600 (trade names of theepoxy(meth)acrylate-based oligomers produced Daicel UCB KabushikKaisha); and the like.

The (meth)acrylate-based adhesive composition used in the presentinvention contains an (C) acrylamide derivative. By incorporating the(C) acrylamide derivative as a reactive monomer to the(meth)acrylate-based adhesive composition, the humidity resistance,water resistance, adhesive force, processability and transparency areimproved. Any of various types of (C) acrylamide derivative is usablewith no specific limitation. Examples of the acrylamide derivativeinclude alkylacrylamide and/or alkylmethacrylamide. Specific examples ofthe acrylamide derivative include acrylamide, methacrylamide,diacetoneacrylamide, diacetonemethacrylamide, alkylenebisacrylamide,dimethylacrylamide, diethylacrylamide, isopropylacrylamide, and4-acrylomorpholine. Dimethylacrylamide, isopropylacrylamide,diethylacrylamide, and 4-acrylomorpholine are more preferable. Thesematerials may be used independently or in a combination of two or more.The content thereof is usually 1 to 50% by weight, and preferably 5 to30% by weight.

The (meth)acrylate-based adhesive composition used in the presentinvention contains a (D) silane compound. The (D) silane compound isused as an adhesion promoter of the (meth)acrylate-based adhesivecomposition, and has an effect of improving the adhesive force and alsoimproving the humidity resistance, water resistance, weather resistanceand transparency. In the present invention, any of various types of (D)silane compound is usable with no specific limitation. Examples of thesilane compound include amino functional silane, epoxy functionalsilane, vinyl functional silane, mercapto functional silane,methacrylate functional silane, acrylamide functional silane, andacrylate functional silane. These materials may be used independently orin a combination of two or more. Among these silane compounds, aminofunctional silane, epoxy functional silane, vinyl functional silane, andmercapto functional silane are especially preferable. Specific examplesof these preferable silane compounds include aminosilanes such asγ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane,N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane, and the like; epoxysilanes suchas (3-(2,3-epoxypropoxy)propyl)trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, andthe like; vinylsilanes such as vinyltris(β-methoxyethoxy)silane,vinyltriethoxysilane, vinyltrimethoxysilane,γ-methacryloxypropyltrimethoxysilane, and the like;hexamethyldisilazane; γ-mercaptopropyltrimethoxysilane; and the like.Among these, epoxysilanes such as(3-(2,3-epoxypropoxy)propyl)trimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilaneare more preferable. (3-(2,3-epoxypropoxy)propyl)trimethoxysilane isespecially preferable. These materials may be used independently or in acombination of two or more. The content thereof is usually 0.1 to 20% byweight, and preferably 1 to 10% by weight.

The (meth)acrylate-based adhesive composition used in the presentinvention contains an (E) organophosphorus compound. The (E)organophosphorus compound is used as an adhesion promoter of the(meth)acrylate-based adhesive composition to a metal compound, and hasan effect of improving the adhesive force to a metal compound and alsoimproving the humidity resistance and water resistance. In the presentinvention, any (E) organophosphorus compound is usable with no specificlimitation, but (meth)acrylate phosphate is especially preferable. Asthe (meth)acrylate phosphate, any (meth)acrylate having a phosphoricacid ester backbone is usable. Examples of such a (meth)acrylatephosphate are not limited to monoester, diester, triester or the like,and include ethylene oxide-denatured phenoxylated(meth)acrylatephosphate, ethylene oxide-denatured butoxylated(meth)acrylate phosphate,ethylene oxide-denatured octyloxylated(meth)acrylate phosphate, ethyleneoxide-denatured di(meth)acrylate phosphate, ethylene oxide-denaturedtri(meth)acrylate phosphate, and the like. In more detail,mono[2-(meth)acryloyloxyethyl]phosphate,mono[2-(meth)acryloyloxyethyl]diphenyl phosphate,mono[2-(meth)acryloyloxypropyl]phosphate,bis[2-(meth)acryloyloxyethyl]phosphate,bis[2-(meth)acryloyloxypropyl]phosphate,tris[2-(meth)acryloyloxyethyl]phosphate and the like are usable. Thesematerials may be used independently or in a combination of two or more.The content thereof is usually 0.1 to 20% by weight, and preferably 1 to10% by weight.

In the present invention, the photoinitiator is used in order topolymerize and cure the (meth)acrylate-based adhesive composition andincrease the curing rate. In the present invention, any generally knownphotoinitiator is usable. Examples of the photoinitiator include2,2-dimethoxy-1,2-diphenylethane-1-one,2-hydroxy-2-methyl-1-phenyl-propane-1-one,1-hydroxy-cyclohexylphenylketone,oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone],bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide 3-methylacetophenone,2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde,fluorene, anthraquinone, triphenylamine, carbazole,3-methylacetophenone, benzophenone, 4-chlorobenzophenone,4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzomethylether,benzoinpropylether, michler's ketone, benzyldimethylketal,1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one,1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one,2,4,6-trimethylbenzoylphenylphosphinate,2,4,6-trimethylbenzoyldiphenylphosphine oxide,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,methylbenzoyl formate, thioxanthone, diethylthioxanthone,2-isopropylthioxanthone, 2-chlorothioxanthone, and the like. Amongthese, 2,2-dimethoxy-1,2-diphenylethane-1-one,2-hydroxy-2-methyl-1-phenyl-propane-1-one,1-hydroxy-cyclohexylphenylketone,oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], andbis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are more preferable.These materials may be used independently or in a combination of two ormore. The content thereof is usually 0.5 to 20% by weight, andpreferably 1 to 10% by weight.

As the photoinitiator, many types are commercially available and easilyobtainable. Specific examples of the photoinitiator include Irgacure184, Irgacure 261, Irgacure 369, Irgacure 379, Irgacure 500, Irgacure651, Irgacure 819, Irgacure 907, Irgacure 1700, Irgacure 1800, Irgacure1850, Irgacure 2959, Irgacure CGI-403, Darocure 953, Darocure 1116,Darocure 1173, Darocure 1664, Darocure 2273, and Darocure 4265 (producedby Ciba Specialty Chemicals), and the like.

As the polymerization initiator for the (meth)acrylate-based adhesivecomposition used in the present invention, a thermal polymerizationinitiator is also usable. An example of the usable thermalpolymerization initiator is selected from azo compounds such as2,2′-azobis(isobutylonitrile) and the like; hydroperoxides such ast-butylhydroperoxide and the like; and peroxides such as benzoylperoxide, cyclohexanone peroxide, and the like. The usable thermalpolymerization initiator is not limited to these. These materials may beused independently or in a combination of two or more.

In addition to the photoinitiator, at least one type of photosensitizermay be optionally added to the (meth)acrylate-based adhesive compositionto control the curing time and curing state. The photosensitizer may beselected from amine compound, urea compound, phosphorus compound,nitrile compound, benzoin compound, carbonyl compound, sulfur compound,naphthalene-based compound, condensed aromatic hydrocarbon and mixturesthereof. Specific examples of the photosensitizer include aminecompounds such as triethylamine, diethylaminoethyl methacrylate,N-methyldiethanolamine, and the like; benzoin compounds such as4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, benzoin,benzoinmethylether, benzomethylether, benzoinisobutylether,benzoinoctylether, and the like; carbonyl compounds such as benzyl,diacetyl, diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone,4′-isopropyl-2-hydroxy-2-methylpropiophenone, methylanthraquinone,acetophenone, benzophenone, benzoyl methyl formate, benzyldimethylketal,1-hydroxycyclohexylphenylketone,2-methyl-1-(4-(methylthio)phenyl)-2-morpholino)-propene-1,2,2-dimethoxy-2-phenylacetophenone,and the like; sulfur compounds such as diphenyldisulfide,dithiocarbamate, and the like; naphthalene-based compounds such asα-chlormethylnaphthalene, and the like; condensed aromatic hydrocarbonssuch as anthracene, and the like; and metal salts such as iron chloride,and the like. These materials may be used independently or in acombination of two or more. The content thereof is usually 0.1 to 5% byweight, and preferably 0.5 to 3% by weight. As the above-mentionedphotosensitizer, a material which has a superb solubility in the(meth)acrylate-based adhesive composition and does not inhibit theultraviolet transmissivity thereof is preferable.

To the (meth)acrylate-based adhesive composition used in the presentinvention, a photostabilizer and an antioxidant may be added in order toprevent aging by hydrolysis or oxidation of the adhesive compositionitself or to improve the heat resistance, weather resistance and thelike under severe conditions of being exposed to sunlight or wind andrain.

Examples of a hindered amine-based photostabilizer includebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, 1-methyl-8-(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate,1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine,4-benzoyloxy-2,2,6,6-tetramethylpiperidine,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,triethylenediamine,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione,and the like.

Examples of a usable nickel-based ultraviolet stabilizer include[2,2′-thiobis(4-t-octylphenolate)]-2-ethylhexylaminenickel(II), nickelcomplex-3,5-di-t-butyl-4-hydroxybenzyl-monoethylate phosphate,nickel-dibutyl-dithiocarbamate, and the like. Especially, a preferablehindered amine-based photostabilizer contains only tertiary amine.Specific examples of such a preferable hindered amine-basedphotostabilizer include bis(1,2,2,6,6-pentamethyl-4-piperidyl)-sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and a condensate of1,2,2,6,6-pentamethyl-4-piperidinol/tridecyl alcohol and1,2,3,4-butanetetracarboxylic acid.

As an antioxidant, it is preferable to use phenol-based antioxidant,thiol-based antioxidant, or phosphite-based antioxidant. Examples of thephenol-based antioxidant include1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,2,2′-methylenebis(4-ethyl-6-t-butylphenol),tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane,2,6-di-t-butyl-p-cresol, 4,4′-thiobis(3-methyl-6-t-butylphenol),4,4′-butylidene bis(3-methyl-6-t-butylphenol),1,3,5-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione,stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,triethyleneglycoibis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],3,9-bis[1,1-di-methyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, andthe like. Especially, a phenol-based antioxidant having a molecularweight of 550 or greater is preferable.

Examples of the thiol-based antioxidant includedistearyl-3,3′-thiodipropionate,pentaerythritol-tetrakis-(β-lauryl-thiopropionate), and the like.Examples of the phosphite-based antioxidant includetris(2,4-di-t-butylphenyl)phosphite,distearylpentaerythritoldiphosphite,di(2,6-di-t-butylphenyl)pentaerythritoldiphosphite,bis-(2,6-di-t-butyl-4-methylphenyl)-pentaerythritoldiphosphite,tetrakis(2,4-di-t-butylphenyl)4,4′-biphenylene-diphosphonite,2,2′-methylenebis(4,6-di-t-butylphenyl)octylphosphite, and the like.

These photostabilizers and antioxidants may be used independently or ina combination of two or more. Especially, a combination of a hinderedamine-based photostabilizer and a hindered phenol-based antioxidant ispreferable. The content thereof is usually 0.1 to 10% by weight, andpreferably 0.5 to 3% by weight. As each of the above-mentionedphotostabilizer and antioxidant, a material which has a superbsolubility in the (meth)acrylate-based adhesive composition and does notinhibit the ultraviolet transmissivity thereof is preferable.

To the (meth)acrylate-based adhesive composition used in the presentinvention, a ultraviolet absorber may be added in order to preventdeterioration by sunlight or ultraviolet. Examples of the ultravioletabsorber include benzophenone-based, benzotriazole-based, phenylsalicylate-based, triazine-based ultraviolet absorbers.

Examples of the benzophenone-based ultraviolet absorber include2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone,2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodesiloxy-benzophenone,2-hydroxy-4-octadesiloxy-benzophenone,2,2′-dihydroxy-4-methoxy-benzophenone,2,2′-dihydroxy-4,4′-dimethoxy-benzophenone,2,2′,4,4′-tetrahydroxy-benzophenone, and the like.

Examples of the benzotriazole-based ultraviolet absorber include2-(2′-hydroxy-5-methylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)benzotriazole, and the like.

Examples of the phenyl salicylate-based ultraviolet absorber includephenyl salicylate, 2-4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like. Examples of a hindered amine-based ultravioletabsorber include bis(2,2,6,6-tetramethylpiperidine-4-yl)sebacate, andthe like.

Examples of the triazine-based ultraviolet absorber include2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine,2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine,2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine,2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine, and thelike.

Examples of the ultraviolet absorber include, in addition to theabove-mentioned materials, compounds having a function of converting anenergy of the ultraviolet into a vibrating energy in the moleculesthereof and releasing the vibrating energy as a thermal energy or thelike. Moreover, a material exhibiting an effect when used together withan antioxidant, a colorant or the like, or a photostabilizer called“quencher” which acts like a photoenergy converter, may be used togetherwith the ultraviolet absorber. It should be noted that when any of theabove-mentioned ultraviolet absorbers is used, an ultraviolet absorberhaving a photo-absorbing wavelength which does not overlap the effectivewavelength of the photoinitiator needs to be selected. When a usualultraviolet blocking agent is used, a photoinitiator generating aradical with visible light is effectively usable.

The amount of the ultraviolet absorber is usually 0.1 to 20% by weight,preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.When the amount of the ultraviolet absorber is larger than 20% byweight, the adhesiveness is poor, and when the ultraviolet absorber issmaller than 0.1% by weight, the effect of improving the weatherresistance is poor.

To the (meth)acrylate-based adhesive composition used in the presentinvention, various other additives may be added. For example, defoamingagent, leveling agent, antistatic agent, surfactant, storage stabilizer,thermal polymerization inhibitor, plasticizer, wettability improvingagent, adhesiveness adding agent, viscosity adding agent, and the likemay be optionally added.

A method for preparing the (meth)acrylate-based adhesive compositionused in the present invention is, for example, as follows. Thecomponents of a (meth)acrylate-based polymerizable oligomer, a(meth)acrylate-based polymerizable monomer, a (A) (meth)acrylatemonomer, a (B) (meth)acrylate oligomer, an (C) acrylamide derivative, a(D) silane compound, an (E) organophosphorus compound, an initiator, asensitizer, other additives, or the like are put into a container, mixedand dissolved at room temperature to 80° C., and optionally filtratedthrough a filter to obtain a desired adhesive composition. For preparingthe adhesive composition, a known method is usable and is not limited tothe above-described method. In consideration of the ease of application,it is preferable that the content ratio of each component of theadhesive composition used in the present invention is appropriatelyadjusted such that the adhesive composition has a viscosity of 1 to 5000mPa at 25° C.

The (meth)acrylate-based adhesive composition used in the presentinvention may be applied by a known method such as use of an applicator,roll knife coat method, die coater method, roll coat method, bar coatmethod, gravure roll coat method, reverse roll coat method, dippingmethod, spray method, curtain flow method, screen coat method, or thelike. The thickness of the adhesive is preferably 2 μm or greater and200 μm or less.

The (meth)acrylate-based adhesive composition used in the presentinvention may be cured by visible light, ultraviolet (UV) or electronbeam (EB). When the visible light or ultraviolet is used, a preferablyused light source is, for example, low pressure mercury lamp, mediumpressure mercury lamp, high pressure mercury lamp, super high pressuremercury lamp, xenon mercury lamp, xenon lamp, gallium lamp, metal halidelamp, quartz halogen lamp, tungsten lamp, ultraviolet fluorescent lamp,carbon arc lamp, electroless microwave system ultraviolet lamp, or thelike.

A specific method of manufacturing an optically transparentelectromagnetic wave shield laminate according to the present inventionis, for example, as follows. A predetermined photocurable adhesive isapplied to a polycarbonate resin sheet by a flow coater, and anelectromagnetic wave shield layer having a polycarbonate resin film as asubstrate is laminated thereon by a laminator such that theelectromagnetic wave shield layer does not contain air bubbles. Then,the resultant assembly of layers is irradiated with a high pressuremercury lamp to cure the adhesive. Thus, the laminate is produced. Inthe case where three or more layers are laminated, an adhesive may beapplied to each layer and irradiated with light, and then the pluralityof layers may be laminated. Alternatively, an adhesive is providedbetween the plurality of layers and then the assembly of layers isirradiated with light to cure the adhesive, thus to produce thelaminate. The laminate preferably has a thickness in the range of 0.1 to30 mm, and more preferably in the range of 0.1 to 20 mm.

The optically transparent electromagnetic wave shield laminate accordingto the present invention may be bent under the following conditions.While a temperature difference between a top surface and a bottomsurface of the shield laminate is controlled to be within 20° C., theshield laminate heated at a temperature of 130 to 185° C. (preferably150 to 185° C.) for 30 seconds to 20 minutes is bent to have a curvedshape having a radius of curvature of 10 mm or greater (preferably 15 to2000 mm). According to a preferable embodiment of the present invention,a good optically transparent electromagnetic wave shield laminate whichis not peeled off, foamed or whitened due to the deterioration ordecomposition of the adhesive layer can be obtained. When thetemperature difference between the top and bottom surfaces exceeds 20°C., the laminate is warped due to the difference in the thermalexpansion. As a result, the layers are peeled off or the adhesive layerbecomes wave-shaped, and thus the laminate becomes defective. Inaddition, since the stress strain remains, the layers are peeled off orcracked, or other faults occur, after being used for a long time. Whenthe heating temperature is lower than 130° C., the polycarbonate resinsubstrate is not sufficiently softened, and therefore, a desired radiusof curvature is not obtained due to springback. By contrast, when theheating temperature exceeds 185° C. (occasionally 165° C.), the adhesiveforce between the electromagnetic wave shield layer and thepolycarbonate resin substrate (protecting layer) is lowered, and thelayers are peeled off, which makes the laminate defective. When theradius of curvature is less than 10 mm, the laminate is excessivelycurved and is likely to be peeled off, which makes the laminatedefective.

The polycarbonate resin laminate according to the present invention isbent under the following conditions. While a temperature differencebetween a top surface and a bottom surface of the polycarbonate resinlaminate is controlled to be within 20° C., the polycarbonate resinlaminate heated to a temperature of 130 to 185° C. (preferably 150 to185° C.) is bent to have a curved shape having a radius of curvature of10 mm or greater (preferably 15 to 2000 mm). The heating time ispreferably 30 seconds to 20 min. According to a preferable embodiment ofthe present invention, a good polycarbonate resin laminate which is notpeeled off, foamed or whitened due to the deterioration or decompositionof the adhesive layer can be obtained. When the temperature differencebetween the top and bottom surfaces exceeds 20° C., the laminate iswarped due to the difference in the thermal expansion. As a result, thelayers are peeled off or the adhesive layer becomes wave-shaped, andthus the laminate becomes defective. When the heating temperature islower than 130° C., the polycarbonate resin substrate is notsufficiently softened, and therefore, a desired radius of curvature isnot obtained due to springback. By contrast, when the heatingtemperature exceeds 185° C., the adhesive force between thepolycarbonate resin substrates is lowered, and the layers are peeledoff, which makes the laminate defective. When the radius of curvature isless than 10 mm, the laminate is excessively curved and is likely to bepeeled off, which makes the laminate defective.

The polycarbonate resin laminate and the optically transparentelectromagnetic wave shield laminate according to the present inventionare each bent, for example, as follows. The laminate is heated to apredetermined temperature using rod-like heater heating, far-infraredheater heating, far-infrared lamp heating, high frequency heating,dielectric heating, induction heating, microwave heating, multi-stagepress heating, electric oven heating, die heating or the like, and thenis bent using a wooden die, a metal die or the like with which apredetermined radius of curvature is obtained. Alternatively, vacuummolding, press molding or the like is usable, but the method of bendingis not limited to these methods.

In each of the polycarbonate resin laminate and the opticallytransparent electromagnetic wave shield laminate according to thepresent invention, at least one layer selected from the electromagneticwave shield layer, the protecting layer and the adhesive layer whichform the polycarbonate resin laminate or the optically transparentelectromagnetic wave shield laminate preferably contains at least one ofan ultraviolet absorber, a photostabilizer and an antioxidant. Such anagent is contained in order to prevent aging by hydrolysis or oxidationof the optically transparent organic polymer materials themselvescontained in the laminate, to prevent deterioration by ultraviolet, orto improve the heat resistance and weather resistance under severeconditions of being exposed to sunlight or wind and rain, or the like.It is preferable that all the layers included in the polycarbonate resinlaminate and the optically transparent electromagnetic wave shieldlaminate each contain at least one of an ultraviolet absorber, aphotostabilizer and an antioxidant, but this is costly and not veryeconomical because the ultraviolet absorber, the photostabilizer and theantioxidant are expensive. In consideration of the cost effectiveness,it is preferable to form a cover film containing at least one of theultraviolet absorber, photostabilizer and antioxidant on one or both ofsurfaces of the polycarbonate resin laminate or the opticallytransparent electromagnetic wave shield laminate.

A cover film containing at least one of the ultraviolet absorber,photostabilizer and antioxidant is preferably formed of a silicone-basedresin compound having a high durability against long-time use and arelatively high surface hardness, or an acrylic resin or apolyfunctional acrylic resin, which is relatively easy to be treated andprovides a good cover film. The method for curing such a cover filmvaries in accordance with the properties of the resin compound used. Inconsideration of the productivity and convenience, it is preferable toselect a thermosetting or photocurable resin. An example of thephotocurable resin is a resin composition formed of a single or aplurality of types of resins such as mono-functional or polyfunctionalacrylate monomer, oligomer or the like, to which a photoinitiator isadded as a curing catalyst. Examples of the thermosetting resin includepolyorganosiloxane-based resin, crosslinked acrylic-based resin, and thelike. Such a resin composition is commercially available as a hard coat,and an appropriate type may be selected in consideration of thecompatibility with the material of the cover film.

To such a cover film, in addition to the above-described ultravioletabsorber, photostabilizer, and antioxidant, various types of stabilizerssuch as organic solvent, anti-coloring agent and the like; levelingagent; defoaming agent; thickener; antistatic agent; surfactants such asantifogging agent and the like; etc. may be optionally added.

The cover film containing at least one of the ultraviolet absorber,photostabilizer and antioxidant may be formed on an acrylic resin layerlaminated on the substrate by coextrusion of a substrate and an acrylicresin in order to improve the adhesiveness of the optically transparentelectromagnetic wave shield laminate with the substrate.

An example of a photocurable acrylic-based resin compound used forforming the cover film is an ultraviolet-curable resin composition forcover film obtained by adding a photoinitiator at 1 to 10% by weight toa photopolymerizable compound formed of 20 to 80% by weight of1,9-nonanediol diacrylate or tris(acroxyethyl)isocyanurate and 20 to 80%by weight of another compound copolymerizable therewith.

Examples of the compound copolymerizable with 1,9-nonanediol diacrylateor tris(acroxyethyl)isocyanurate used as indispensable componentsinclude at least bi-functional polyfunctional (meth)acrylate monomer,and at least bi-functional polyfunctional urethane(meth)acrylateoligomer (hereinafter, referred to as the “polyfunctionalurethane(meth)acrylate oligomer”), at least bi-functional polyfunctionalpolyester(meth)acrylate oligomer (hereinafter, referred to as the“polyfunctional polyester(meth)acrylate oligomer”), at leastbi-functional polyfunctional epoxy(meth)acrylate oligomer (hereinafter,referred to as the “polyfunctional epoxy(meth)acrylate oligomer”) andthe like. A single type of, or a combination of two or more types of,the (meth)acrylate monomer or oligomer is usable.

Representative examples of the bi-functional (meth)acrylate monomerinclude alkyleneglycol di(meth)acrylates, polyoxyalkyleneglycoldi(meth)acrylates, halogen-substituted alkyleneglycol di(meth)acrylates,di(meth)acrylate of fatty acid polyol, alkylene oxide-adductdi(meth)acrylates of bisphenol A or bisphenol F, epoxy di(meth)acrylatesof bisphenol A or bisphenol F, and the like. The bi-functional(meth)acrylate monomer is not limited to these, and various othermaterials are usable. Specific examples of the bi-functional(meth)acrylate monomer include 2-n-butyl-2-ethyl-1,3-propanedioldiacrylate, tripropyleneglycol diacrylate, tetraethyleneglycoldiacrylate, polyethyleneglycol di(meth)acrylate, polypropyleneglycoldiacrylate, triethyleneglycol dimethacrylate, 1,6-hexanedioldimethacrylate, neopentylglycol dimethacrylate, and the like. Examplesof the at least tri-functional (meth)acrylate monomer includetrimethylolpropane trimethacrylate, trimethylolpropaneethyleneoxide-adduct triacrylate, glycerinpropylene oxide-adduct triacrylate,pentaerythritol tetraacrylate, and the like.

An example of the polyfunctional urethane(meth)acrylate oligomer is aurethanization reaction product of a (meth)acrylate monomer having atleast one (meth)acryloyloxy group and at least one hydroxyl group in onemolecule and a polyisocyanate. An example of the polyfunctionalurethane(meth)acrylate oligomer is a urethanization reaction product ofan isocyanate compound obtained by reacting a polyol with polyisocyanateand a (meth)acrylate monomer having at least one (meth)acryloyloxy groupand at least one hydroxyl group in one molecule.

Examples of the (meth)acrylate monomer having at least one(meth)acryloyloxy group and at least one hydroxyl group in one molecule,which is used for the urethanization reaction, include2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,2-hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate,glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate,pentaerythritol tri(meth)acrylate, dipentaerythritolpenta(meth)acrylate, and the like.

Examples of the polyisocyanate used for the urethanization reactioninclude di- or tri-isocyanate such as hexamethylene diisocyanate, lysinediisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate,tolylene diisocyanate, xylylene diisocyanate, diisocyanate (among thesediisocyanates) obtained by adding hydrogen to aromatic isocyanate (e.g.,diisocyanate such as hydrogen-added tolylene diisocyanate,hydrogen-added xylylene diisocyanate, or the like), triphenylmethanetriisocyanate, dimethylenetriphenyl triisocyanate and the like; andpolyisocyanate obtained by multimerization of diisocyanate.

Example of the polyol generally used for the urethanization reactioninclude aromatic, aliphatic and alicyclic polyols, and also polyesterpolyol, polyether polyol, and the like. Usually, examples of thealiphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol,neopentylglycol, ethyleneglycol, propyleneglycol, trimethylolethane,trimethylolpropane, dimethylolheptane, dimethylolpropionic acid,dimethylolbutylionic acid, glycerin, water-added bisphenol A, and thelike.

Polyester polyol is obtained by dehydrogenation-condensation reaction ofa polyol described above and a polybasic carboxylic acid (anhydride).Specific examples of the polybasic carboxylic acid include succinic acid(anhydride), adipic acid, maleic acid (anhydride), trimellitic acid(anhydride), hexahydrophthalic acid (anhydride), phthalic acid(anhydride), isophthalic acid, terephthalic acid, and the like. Examplesof the polyether polyol include polyalkyleneglycol, andpolyoxyalkylene-denatured polyol obtained by the reaction of a polyol orphenol with alkylene oxide.

The polyfunctional polyester(meth)acrylate oligomer is obtained bydehydrogenation-condensation reaction of a (meth)acrylic acid, apolybasic carboxylic acid (anhydride) and a polyol. Examples of thepolybasic carboxylic acid (anhydride) used for thedehydrogenation-condensation reaction include succinic acid (anhydride),adipic acid, maleic acid (anhydride), itaconic acid (anhydride),trimellitic acid (anhydride), pyromellitic acid (anhydride),hexahydrophthalic acid (anhydride), phthalic acid (anhydride),isophthalic acid, terephthalic acid, and the like. Examples of thepolyol used for the dehydrogenation-condensation reaction include1,4-butanediol, 1,6-hexanediol, diethyleneglycol, triethyleneglycol,propyleneglycol, neopentylglycol, dimethylolheptane, dimethylolpropionicacid, dimethylolbutylionic acid, trimethylolpropane,ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.

The polyfunctional epoxy(meth)acrylate oligomer is obtained by additionreaction of a polyglycidylether and a (meth)acrylic acid. Examples ofthe polyglycidylether include ethyleneglycoldiglycidylether,propyleneglycoldiglycidylether, tripropyleneglycoldiglycidylether,1,6-hexanedioldiglycidylether, bisphenol A diglycidylether, and thelike.

As the photoinitiator used for the cover film formed of a photocurableacrylic-based resin compound, any generally known photoinitiator isusable. Examples of such a photoinitiator include, but are not limitedto, benzoin, benzophenone, benzomethylether, benzoinisopropylether,2,2-dimethoxy-2-phenylacetophonone, 1-hydroxycyclohexylphenylketone,2-hydroxy-2-methyl-1-phenylpropane-1-one, azobisisobutylonitrile,benzoylperoxide, and the like.

A specific example of the cover film formed of a thermosettingsilicone-based resin compound is an organopolysiloxane-based resincompound containing at least one of epoxy-containing silane couplingagent and an amino-containing silane coupling agent. In more detail, acured layer formed of an organopolysiloxane-based resin compoundobtained as follows is an example of the cover film. A resin compound,formed of alkoxysilane containing 0 to 25% by weight of bi-functionalalkoxysilane, 40 to 80% by weight of tri-functional alkoxysilane, and 10to 25% by weight of tetra-functional alkoxysilane with respect to thenonvolatile content of the resin compound (JIS K6833), is mixed with 5to 10% by weight of at least one of an epoxy-containing silane couplingagent and an amino-containing silane coupling agent; and this mixture istreated with hydrolysis and partial condensation in a solvent under thepresence of an acid catalyst. Thus, the cured layer formed of anorganopolysiloxane-based resin compound is obtained.

Examples of the bi-functional alkoxysilane used for forming theorganopolysiloxane-based resin compound include dimethyldimethoxysilane,dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,and the like. Examples of the tri-functional alkoxysilane used forforming the organopolysiloxane-based resin compound includemethyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, andthe like. Examples of the tetra-functional alkoxysilane used for formingthe organopolysiloxane-based resin compound include tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, and the like.

The mixing ratios of the alkoxysilanes are preferably as follows: 0 to25% by weight of the bi-functional alkoxysilane, 40 to 80% by weight ofthe tri-functional alkoxysilane, and 10 to 25% by weight of thetetra-functional alkoxysilane with respect to the nonvolatile content ofthe material applied for forming the cover film (JIS K6833). When thebi-functional alkoxysilane is contained at more than 25% by weight orthe tri-functional alkoxysilane is contained at more than 80%, theabrasion resistance is lowered. When the tetra-functional alkoxysilaneis contained at more than 30% by weight, the adhesiveness with thesubstrate is poor, whereas when the tetra-functional alkoxysilane iscontained at less than 10% by weight, the abrasion resistance islowered.

A preferable example of the silane coupling agent used for forming theorganopolysiloxane-based resin compound is at least one of anepoxy-containing silane coupling agent and an amino-containing silanecoupling agent. The silane coupling agent is used in the range of 5 to10% by weight with respect to the nonvolatile content of the materialapplied for forming the cover film (JIS K6833). When the silane couplingagent is used at less than 5% by weight, the film properties andadhesiveness are lowered, whereas when the silane coupling agent is usedat more than 10% by weight, the abrasion resistance is lowered.

Examples of the epoxy-containing silane coupling agent used for formingthe organopolysiloxane-based resin compound include3-glycidoxypropylmethyldimethoxysilane,3-glycidoxypropyltrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like. Examples ofthe amino-containing silane coupling agent used for forming theorganopolysiloxane-based resin compound includeN-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, and the like.

The organopolysiloxane-based resin compound is produced by treating themixture of the alkoxysilane and the silane coupling agent withhydrolysis and partial condensation using lower alcohol and/or waterunder the presence of an acid catalyst. As the lower alcohol, methanol,ethanol, isopropanol, butanol, or the like is usable.

Together with the organopolysiloxane-based resin compound, avinyl-containing silane coupling agent such as vinyltrimethoxysilane,vinyltriethoxysilane or the like, or a methacryloxy-containing silanecoupling agent such as 3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane or the like is usable in such arange that the properties of the organopolysiloxane-based resin compoundare not spoiled.

To the silane coupling agent-containing organopolysiloxane-based resincompound, it is preferable to add a curing catalyst provided with abuffer solution such that a cured film is obtained at a temperature of120 to 140° C. Examples of the curing catalyst include dimethylamine,ethanolamine acetate, dimethylaniline formate, tetraethylammoniumbenzoate salt, sodium acetate, sodium propionate, sodium formate,benzoyltrimethylammonium acetate salt, tetramethylammonium acetate, andthe like. The amount of the curing catalyst is in the range of 0.1 to 1%by weight with respect to the nonvolatile content of the resin compound.

In order to improve the adhesiveness of the cover film, used in thepresent invention, containing at least one of the ultraviolet absorber,the photostabilizer and the antioxidant, a primer layer may be formed.Examples of the compound used for forming the primer layer includeacrylic group-containing organic compound, condensate of acrylicgroup-containing silane compound, condensate of alkoxysilylgroup-containing vinyl-based compound, and the like. Examples of theacrylic group-containing compound include alkylacrylates such as methylmethacrylate, 2-hydroxyethyl methacrylate, butyl methacrylate, ethylacrylate and the like, etc.

Examples of the acrylic group-containing silane compound include3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,3-acryloxypropylmethyldimethoxysilane,3-acryloxypropylmethyldiethoxysilane,3-methacryloxymethyltrimethoxysilane,3-methacryloxymethyltriethoxysilane,3-methacryloxymethylmethyldimethoxysilane,3-methacryloxymethylmethyldiethoxysilane,3-acryloxymethyltrimethoxysilane, 3-acryloxymethyltriethoxysilane,3-acryloxymethylmethyldimethoxysilane,3-acryloxymethylmethyldiethoxysilane, and the like. Among these,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-acryloxypropyltrimethoxysilane, and3-acryloxypropylmethyldimethoxysilane are preferable in terms of ease ofhandling, crosslinking density, reactivity, and the like. Examples ofthe alkoxysilyl group-containing vinyl-based monomer includevinyltrimethoxysilane, vinyltriethoxysilane,vinyltris(2-methoxyethoxy)silane, vinylmethyldimethoxysilane,vinylmethyldiethoxysilane, vinylmethylbis(2-methoxyethoxy)silane,3-vinyloxypropyltrimethoxysilane, 3-vinyloxypropyltriethoxysilane,3-vinyloxypropylmethyldimethoxysilane,3-vinyloxypropylmethyldiethoxysilane, stylyltrimethoxysilane,stylyltriethoxysilane, stylylmethyldimethoxysilane,stylylmethyldiethoxysilane, and the like. Among these,vinyltrimethoxysilane, vinyltriethoxysilane, and3-vinyloxypropyltrimethoxysilane are preferable in terms of ease ofhandling, reactivity and the like.

According to the present invention, the cover film may be applied on thepolycarbonate resin laminate by means of brush, roll, dipping, flowcoating, spray, roll coater, flow coater or the like. The thickness ofthe cover film layer cured by thermal curing or photocuring is 1 to 20μm, preferably 2 to 15 μm, and more preferably 3 to 12 μm. When thethickness of the cover film layer is less than 1 μm, the effects ofimproving the weather resistance and the surface hardness are likely tobe insufficient, whereas a thickness exceeding 20 μm is disadvantageousin terms of cost and may lower the impact resistance.

EXAMPLES

Hereinafter, embodiments and effects of the present invention will bespecifically described by way of examples and comparative examples. Thepresent invention is not limited to these specific embodiments orexamples in any way. The evaluation results described in the examplesand the comparative examples were obtained by the following tests.

(Adhesive Force Test)

The adhesive force of a sample was measured in conformity to the 180degree peel strength test of adhesiveness (JIS K6854-2) or the T-peelstrength test of adhesiveness (JIS K6854-3). Specifically, polycarbonateresin sheets or films were bonded to each other with each of variousadhesive compositions to produce a test piece having a width of 25 mmand a length of 200 mm. The peel strength [N/25 mm width] was measuredby a tensile tester (AGS-100G produced by Shimadzu Corporation) at apeeling rate of 10 mm/min.

(Humidity Resistance Test)

A sample was put into a constant temperature and humidity chamber of 65°C. and 95% RH and cooled back to room temperature after being treatedfor 200 hours. The transparency was visually evaluated.

[Visual Evaluation]

-   ◯: Good transparency, no change-   Δ: Slightly cloudy, visible-   X: Cloudy, not visible    (Bendability Test)

Polycarbonate resin sheets or films were bonded to each other with eachof various adhesive compositions to produce a test piece having a widthof 25 mm and a length of 200 mm. The test piece was heated from aboveand below by a far-infrared heater. After the surface temperature of thetest piece reached a predetermined temperature, the test piece was bentusing a die having a predetermined radius of curvature. The radius ofcurvature and the bending state of the test piece were visuallyevaluated.

[External Appearance Evaluation]

-   ◯: No abnormality in the external appearance-   X: Either peeled off, foamed, whitened, warped or wave-shaped    [Evaluation of the Radius of Curvature of the Test Piece]-   ◯: Error is within 10% with respect to the radius of curvature of    the die-   Δ: Error is within 20% with respect to the radius of curvature of    the die-   X: Error is 20% or greater with respect to the radius of curvature    of the die, or unmeasurable    (Method for Preparing an Adhesive)

The components of a (A) (meth)acrylate monomer, a (B) (meth)acrylateoligomer, an (C) acrylamide derivative, a (D) silane compound, an (E)organophosphorus compound, a photoinitiator and the like were put into acontainer at each of compositions shown in Table 1, and mixed and heatedat 60° C. for 1 hour. Thus, a desired adhesive composition was obtained.The components used for the adhesive composition are as follows.

[Components of the Adhesive Composition]

-   -   Urethane(meth)acrylate-based polymerizable oligomer:        Dicyclohexylmethanediisocyanate-derived alicyclic hydrocarbon        compound-containing urethane(meth)acrylate-based oligomer    -   (Meth)acrylate-based polymerizable monomer: Isobornyl acrylate    -   Acrylamide derivative: Dimethylacrylamide    -   Silane compound: (3-(2,3-epoxypropoxy)propyl)trimethoxysilane    -   Organophosphorus compound: Acrylate phosphate    -   Photoinitiator: Irgacure 651        (Method for Producing a Polycarbonate Resin Laminate Using an        Optically Transparent Adhesive)

Each of various adhesive compositions was applied on a polycarbonateresin sheet or film as a first layer by a bar coater, and apolycarbonate resin sheet or film as a second layer was laminatedthereon by a laminator while being defoamed. This sample was irradiatedwith a high pressure mercury lamp (500 W) for 90 seconds and thus wassufficiently cured at a radiation amount of 1 J/cm². In the case where apolycarbonate resin sheet or film as a third layer was laminated,substantially the same method was used.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 50 mm and a length of 200 mm. This was used as asample for evaluation.

[Materials]

-   -   PC sheet: Polycarbonate sheet (thickness: 1.5 mm to 20.0 mm)        produced by MGC Filsheet Co., Ltd.    -   PC film: Polycarbonate film (thickness: 100 to 200 μm) produced        by MGC Filsheet Co., Ltd.        (Method for Producing a Polycarbonate Resin Laminate Using a        Hotmelt-type Adhesive)

A hotmelt-type adhesive sheet was sandwiched between a polycarbonateresin sheet as a first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin film as a second layer (PC film; thickness: 200 μm),and the assembly of layers was pressed at 135° C. for 30 minutes.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 50 mm and a length of 200 mm. This was used as asample for evaluation.

[Hotmelt (HM)-type Adhesive]

-   -   Ethylene vinyl acetate (EVA)-based HM-type adhesive: Elphan        OH-501 produced by Nihon Matai, Co., Ltd.    -   Polyamide-based HM-type adhesive: Elphan NT-120 produced by        Nihon Matai, Co., Ltd.    -   Polyurethane-based HM-type adhesive: Kurangile S-1700 produced        by Kurabo Industries, Ltd.    -   Polyester-based HM-type adhesive: Kuranbetter G-6 produced by        Kurabo Industries, Ltd.    -   Polyolefin-based HM-type adhesive: Kuranbetter A-1510 produced        by Kurabo Industries, Ltd.        (Method for Producing a Polycarbonate Resin Laminate Using a        Pressure-sensitive Adhesive)

A pressure-sensitive adhesive sheet was sandwiched between apolycarbonate resin sheet as a first layer (PC sheet; thickness: 3.0 mm)and a polycarbonate resin film as a second layer (PC film; thickness:200 μm), and the assembly of layers was pressed for 5 minutes.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 25 mm and a length of 200 mm. This was used as asample for evaluation.

[Pressure-sensitive Adhesive]

-   -   Acrylic-based pressure-sensitive adhesive sheet: CS-9621        produced by Nitto Denko Corporation

Example 1

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the “adhesive force test” described above, the sample had an adhesiveforce of 150 N. In the “humidity resistance test” described above, thesample exhibited a good result of not being clouded even after beingtreated for 200 hours. The “bendability test” described above wasperformed under the conditions of a surface temperature (top) of 160°C., a surface temperature (bottom) of 160° C., a surface temperaturedifference of 0° C., and a radius of curvature of the die of 25 mm. As aresult, the external appearance was good, and the radius of curvature ofthe test piece was 25 mm.

Example 2

30.4% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.6% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, and4.0% by weight of photoinitiator were put into a container, and anadhesive composition was prepared in accordance with the “method forpreparing an adhesive” described above. The obtained adhesivecomposition was used for a polycarbonate resin first layer (PC sheet;thickness: 3.0 mm) and a polycarbonate resin second layer (PC film;thickness: 200 μm) to produce a sample in accordance with the “methodfor producing a polycarbonate resin laminate using an opticallytransparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 70 N. Inthe humidity resistance test, the sample was not recognized as beingchanged even after being treated for 100 hours, and was slightly cloudedafter being treated for 200 hours. The bendability test was performedunder the conditions of a surface temperature (top) of 160° C., asurface temperature (bottom) of 160° C., a surface temperaturedifference of 0° C., and a radius of curvature of the die of 25 mm. As aresult, the external appearance was good, and the radius of curvature ofthe test piece was 25 mm.

Example 3

32.1% by weight of urethane(meth)acrylate-based polymerizable oligomer,42.9% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 1.0% by weight of organophosphoruscompound, and 4.0% by weight of photoinitiator were put into acontainer, and an adhesive composition was prepared in accordance withthe “method for preparing an adhesive” described above. The obtainedadhesive composition was used for a polycarbonate resin first layer (PCsheet; thickness: 3.0 mm) and a polycarbonate resin second layer (PCfilm; thickness: 200 μm) to produce a sample in accordance with the“method for producing a polycarbonate resin laminate using an opticallytransparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 85 N. Inthe humidity resistance test, the sample was not recognized as beingclouded after being treated for 24 hours, and was slightly clouded afterbeing treated for 100 hours. The bendability test was performed underthe conditions of a surface temperature (top) of 160° C., a surfacetemperature (bottom) of 160° C., a surface temperature difference of 0°C., and a radius of curvature of the die of 25 mm. As a result, theexternal appearance was good, and the radius of curvature of the testpiece was 25 mm.

Example 4

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 130° C., a surface temperature (bottom) of 130° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 29 mm.

Example 5

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 6

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 185° C., a surface temperature (bottom) of 185° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 7

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 160° C., a surface temperature (bottom) of 140° C.,a surface temperature difference of 20° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 8

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 10.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 160° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 50 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 51 mm.

Example 9

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 20.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 160° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 100 mm. As a result, the external appearance was good, andthe radius of curvature of the test piece was 105 mm.

Example 10

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 160° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 10 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 11 mm.

Example 11

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin second layer (PC film; thickness: 200 μm) andpolycarbonate resin first and third layers (PC sheet; thickness: 1.5 mmeach) provided above and below the second layer to produce a sample inaccordance with the “method for producing a polycarbonate resin laminateusing an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 160° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 26 mm.

Comparative Example 1

41.1% by weight of urethane(meth)acrylate-based polymerizable oligomer,54.9% by weight of (meth)acrylate-based polymerizable monomer, and 4.0%by weight of photoinitiator were put into a container, and an adhesivecomposition was prepared in accordance with the “method for preparing anadhesive” described above. The obtained adhesive composition was usedfor a polycarbonate resin first layer (PC sheet; thickness: 3.0 mm) anda polycarbonate resin second layer (PC film; thickness: 200 μm) toproduce a sample in accordance with the “method for producing apolycarbonate resin laminate using an optically transparent adhesive”described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 1 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 24 hours. The bendability test was performed under the conditions ofa surface temperature (top) of 160° C., a surface temperature (bottom)of 160° C., a surface temperature difference of 0° C., and a radius ofcurvature of the die of 25 mm. As a result, peel-off occurred.

Comparative Example 2

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 190° C., a surface temperature (bottom) of 190° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer became wave-shaped,and the radius of curvature of the test piece was 25 mm.

Comparative Example 3

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing a polycarbonateresin laminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 150 N.In the humidity resistance test, the sample exhibited a good result ofnot being clouded even after being treated for 200 hours. Thebendability test was performed under the conditions of a surfacetemperature (top) of 170° C., a surface temperature (bottom) of 140° C.,a surface temperature difference of 30° C., and a radius of curvature ofthe die of 25 mm. As a result, the external shape was warped, and theradius of curvature of the test piece was 25 mm.

Comparative Example 4

A visible-light curable adhesive (BENEFIX PC produced by AdellCorporation) was used for a polycarbonate resin first layer (PC sheet;thickness: 3.0 mm) and a polycarbonate resin second layer (PC film;thickness: 200 μm) to produce a sample in accordance with the “methodfor producing a polycarbonate resin laminate using an opticallytransparent adhesive” described above. The adhesive was cured using avisible-light fluorescent lamp as the light source.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 30 N, atwhich the PC film was ruptured. In the humidity resistance test, thesample was clouded after being treated for 24 hours. The bendabilitytest was performed under the conditions of a surface temperature (top)of 160° C., a surface temperature (bottom) of 160° C., a surfacetemperature difference of 0° C., and a radius of curvature of the die of25 mm. As a result, the external appearance was good, and the radius ofcurvature of the test piece was 26 mm.

Comparative Example 5

An ethylene vinyl acetate (EVA)-based hotmelt-type adhesive wassandwiched between a polycarbonate resin first layer (PC sheet;thickness: 3.0 mm) and a polycarbonate resin second layer (PC film;thickness: 200 μm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a hotmelt-type adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 7 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 24 hours. The bendability test was performed under the conditions ofa surface temperature (top) of 160° C., a surface temperature (bottom)of 160° C., a surface temperature difference of 0° C., and a radius ofcurvature of the die of 25 mm. As a result, the adhesive layer wasair-bubbled, and peel-off occurred.

Comparative Example 6

A polyamide-based hotmelt-type adhesive was sandwiched between apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing an opticallytransparent electromagnetic wave shield laminate using a hotmelt-typeadhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 2 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 100 hours. The bendability test was performed under the conditionsof a surface temperature (top) of 160° C., a surface temperature(bottom) of 160° C., a surface temperature difference of 0° C., and aradius of curvature of the die of 25 mm. As a result, peel-off occurred.

Comparative Example 7

A polyurethane-based hotmelt-type adhesive was sandwiched between apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing an opticallytransparent electromagnetic wave shield laminate using a hotmelt-typeadhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 92 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 24 hours. The bendability test was performed under the conditions ofa surface temperature (top) of 160° C., a surface temperature (bottom)of 160° C., a surface temperature difference of 0° C., and a radius ofcurvature of the die of 25 mm. As a result, the adhesive layer waswhitened and the visibility was lost.

Comparative Example 8

A polyester-based hotmelt-type adhesive was sandwiched between apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing an opticallytransparent electromagnetic wave shield laminate using a hotmelt-typeadhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 107 N.In the humidity resistance test, the sample was clouded after beingtreated for 24 hours. The bendability test was performed under theconditions of a surface temperature (top) of 160° C., a surfacetemperature (bottom) of 160° C., a surface temperature difference of 0°C., and a radius of curvature of the die of 25 mm. As a result, theadhesive layer was recognized as being foamed, and peel-off occurred.

Comparative Example 9

A polyolefin-based hotmelt-type adhesive was sandwiched between apolycarbonate resin first layer (PC sheet; thickness: 3.0 mm) and apolycarbonate resin second layer (PC film; thickness: 200 μm) to producea sample in accordance with the “method for producing an opticallytransparent electromagnetic wave shield laminate using a hotmelt-typeadhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 3 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 100 hours. The bendability test was performed under the conditionsof a surface temperature (top) of 160° C., a surface temperature(bottom) of 160° C., a surface temperature difference of 0° C., and aradius of curvature of the die of 25 mm. As a result, peel-off occurred.

Comparative Example 10

An acrylic-based pressure-sensitive adhesive sheet was sandwichedbetween a polycarbonate resin first layer (PC sheet; thickness: 3.0 mm)and a polycarbonate resin second layer (PC film; thickness: 200 μm) toproduce a sample in accordance with the “method for producing anoptically transparent electromagnetic wave shield laminate using apressure-sensitive adhesive” described above.

As a result of performing various evaluations, the following was found.In the adhesive force test, the sample had an adhesive force of 6 N. Inthe humidity resistance test, the sample was clouded after being treatedfor 100 hours. The bendability test was performed under the conditionsof a surface temperature (top) of 160° C., a surface temperature(bottom) of 160° C., a surface temperature difference of 0° C., and aradius of curvature of the die of 25 mm. As a result, the adhesive layerwas foamed, and peel-off occurred.

TABLE 1 Polycarbonate resin (Meth)acrylate adhesive composition [% byweight] laminate structure Urethane (Meth)acryl- Acryla- Organo- Film orsheet substrate Adhesive type (meth)acrylate ate poly- mide Silanephospho- (thickness[mm]) Curing Main polymerizable merizable deriv- com-rus Photo- 3rd method component oligomer monomer ative pound compoundinitiator 1st layer 2nd layer layer Ex. 1 Photocurable Acrylic- 30.040.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 2 PhotocurableAcrylic- 30.4 40.6 20.0 5.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 3Photocurable Acrylic- 32.1 42.9 20.0 1.0 4.0 PC(3.0) PC(0.2) adhesivebased Ex. 4 Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0)PC(0.2) adhesive based Ex. 5 Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 6 Photocurable Acrylic- 30.040.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 7 PhotocurableAcrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 8Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0  PC(10.0) PC(0.2)adhesive based Ex. 9 Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(20.0) PC(0.2) adhesive based Ex. 10 Photocurable Acrylic- 30.0 40.020.0 5.0 1.0 4.0 PC(3.0) PC(0.2) adhesive based Ex. 11 PhotocurableAcrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(1.5) PC(0.2) PC(1.5) adhesivebased Compara- Photocurable Acrylic- 41.1 54.9 4.0 PC(3.0) PC(0.2) tiveex. 1 adhesive based Compara- Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(3.0) PC(0.2) tive ex. 2 adhesive based Compara- PhotocurableAcrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) tive ex. 3 adhesivebased Compara- Visible-light Acrylic- PC(3.0) PC(0.2) tive ex. 4 curablebased adhesive (Adell) Compara- Hot melt-type EVA- PC(3.0) PC(0.2) tiveex. 5 adhesive based Compara- Hot melt-type Polyam- PC(3.0) PC(0.2) tiveex. 6 adhesive ide- based Compara- Hot melt-type Polyure- PC(3.0)PC(0.2) tive ex. 7 adhesive thane- based Compara- Hot melt-typePolyester- PC(3.0) PC(0.2) tive ex. 8 adhesive based Compara- Hotmelt-type Polyolefin- PC(3.0) PC(0.2) tive ex. 9 adhesive based Compara-Pressure- Acrylic- PC(3.0) PC(0.2) tive ex. 10 sensitive based adhesive

TABLE 2 Bending conditions Adhesive Heating temperature [° C.] Radiusforce test Bendability test Surface of T-peel Radius of Top Bottomtemper- curva- strength Humidity curvature Adhesive type surface surfaceature ture test resistance test External of test Curing Main temper-temper- differ- of die [N/25 65° C.-95% RH appear- piece methodcomponent ature ature ence [mm] mm] 24 h 100 h 200 h ance [mm] Ex. 1Photocurable Acrylic- 160 160 0 25 150 ◯ ◯ ◯ ◯ 25(◯) adhesive based Ex.2 Photocurable Acrylic- 160 160 0 25 70 ◯ ◯ Δ ◯ 25(◯) adhesive based Ex.3 Photocurable Acrylic- 160 160 0 25 85 ◯ Δ X ◯ 25(◯) adhesive based Ex.4 Photocurable Acrylic- 130 130 0 25 150 ◯ ◯ ◯ ◯ 29(Δ) adhesive basedEx. 5 Photocurable Acrylic- 165 165 0 25 150 ◯ ◯ ◯ ◯ 25(◯) adhesivebased Ex. 6 Photocurable Acrylic- 185 185 0 25 150 ◯ ◯ ◯ ◯ 25(◯)adhesive based Ex. 7 Photocurable Acrylic- 160 140 20 25 150 ◯ ◯ ◯ ◯25(◯) adhesive based Ex. 8 Photocurable Acrylic- 160 160 0 50 150 ◯ ◯ ◯◯ 51(◯) adhesive based Ex. 9 Photocurable Acrylic- 160 160 0 100 150 ◯ ◯◯ ◯ 105(◯)  adhesive based Ex. 10 Photocurable Acrylic- 160 160 0 10 150◯ ◯ ◯ ◯ 11(◯) adhesive based Ex. 11 Photocurable Acrylic- 160 160 0 25150 ◯ ◯ ◯ ◯ 26(◯) adhesive based Compara- Photocurable Acrylic- 160 1600 25 1 X X X X peeled Unmeasur- tive ex. 1 adhesive based off able (X)Compara- Photocurable Acrylic- 190 190 0 25 150 ◯ ◯ ◯ X wave- 25(◯) tiveex. 2 adhesive based shaped Compara- Photocurable Acrylic- 170 140 30 25150 ◯ ◯ ◯ X warped 25(◯) tive ex. 3 adhesive based Compara-Visible-light Acrylic- 160 160 0 25 30(PC X X X ◯ 26(◯) tive ex. 4curable based ruptured adhesive (Adell) Compara- Hot melt-type EVA- 160160 0 25 7 X X X X peeled Unmeasur- tive ex. 5 adhesive based off/foamedable (X) Compara- Hot melt-type Polyam- 160 160 0 25 2 ◯ X X X peeledUnmeasur- tive ex. 6 adhesive ide based off able (X) Compara- Hotmelt-type Polyure- 160 160 0 25 92 X X X X whitened 26(◯) tive ex. 7adhesive thane- based Compara- Hot melt-type Polyester- 160 160 0 25 107X X X X peeled Unmeasur- tive ex. 8 adhesive based off/foamed able (X)Compara- Hot melt-type Polyolefin- 160 160 0 25 3 ◯ X X X peeledUnmeasur- tive ex. 9 adhesive based off able (X) Compara- Pressure-Acrylic- 160 160 0 25 6 ◯ X X X peeled Unmeasur- tive ex. 10 sensitivebased off/foamed able (X) adhesive(Electromagnetic Wave Shield Performance Test)

The electromagnetic wave shield performance in a frequency range of 100MHz to 1 GHz was measured using an electromagnetic wave shieldperformance measuring device (produced by Advantest Corporation).

[Electromagnetic Wave Shield Performance Evaluation]

A sample exhibiting an electromagnetic wave shield performance of 30 dBor greater at the frequencies of 100 MHz and 1 GHz was evaluated as good(◯), and a sample exhibiting an electromagnetic wave shield performanceof less than 30 dB at the frequencies of 100 MHz and 1 GHz was evaluatedas poor (X).

(Adhesive Force Test)

The adhesive force of a sample was measured in conformity to the 180degree peel strength test of adhesiveness (JIS K6854-2). Specifically,an electromagnetic wave shield layer (PC film, PET film) and aprotecting layer (PC sheet or film) were bonded to each other with eachof various adhesive compositions to produce a test piece having a widthof 25 mm and a length of 200 mm. The peel strength [N/25 mm width] wasmeasured by a tensile tester at a peeling rate of 10 mm/min. Theadhesive forces of the adhesive with the electromagnetic wave shieldlayer and the protecting layer (top and bottom surfaces) were measured,and a smaller value was shown in each of the examples and thecomparative examples.

(Bendability Test)

An electromagnetic wave shield layer (PC film, PET film) and aprotecting layer were bonded to each other with each of various adhesivecompositions to produce a test piece having a width of 50 mm and alength of 200 mm. The test piece was heated from above and below by afar-infrared heater. After the surface temperature of the test piecereached a predetermined temperature, the test piece was bent using a diehaving a predetermined radius of curvature. The radius of curvature andthe bending state of the test piece were visually evaluated.

[External Appearance Evaluation]

-   ◯: No abnormality in the external appearance-   X: Either peeled off, foamed, whitened, warped or wave-shaped    [Evaluation of the Radius of Curvature of the Test Piece]-   ◯: Error is within 10% with respect to the radius of curvature of    the die-   Δ: Error is within 20% with respect to the radius of curvature of    the die-   X: Error is 20% or greater with respect to the radius of curvature    of the die, or unmeasurable    (Method for Preparing an Adhesive)

The components of a (A) (meth)acrylate monomer, a (B) (meth)acrylateoligomer, an (C) acrylamide derivative, a (D) silane compound, an (E)organophosphorus compound, a photoinitiator and the like were put into acontainer at each of compositions shown in Tables 3 and 4, and mixed andheated at 60° C. for 1 hour. Thus, a desired adhesive composition wasobtained. The components used for the adhesive composition are asfollows.

[Components of the Adhesive Composition]

-   -   Urethane(meth)acrylate-based polymerizable oligomer:        Dicyclohexylmethanediisocyanate-derived alicyclic hydrocarbon        compound-containing urethane(meth)acrylate-based oligomer    -   (Meth)acrylate-based polymerizable monomer: Isobornyl acrylate    -   Acrylamide derivative: Dimethylacrylamide    -   Silane compound: (3-(2,3-epoxypropoxy)propyl)trimethoxysilane    -   Organophosphorus compound: Acrylate phosphate    -   Photoinitiator: Irgacure 651        (Method for Producing an Optically Transparent Electromagnetic        Wave Shield Laminate Using an Optically Transparent Adhesive)

Each of various adhesive compositions was applied on a protecting layer(PC sheet or film) by a bar coater, and an electromagnetic wave shieldlayer (PC film, PET film) was laminated thereon by a laminator whilebeing defoamed. This sample was irradiated with a high pressure mercurylamp (500 W) for 90 seconds and thus was sufficiently cured at aradiation amount of 1 J/cm². In the case where the protecting layer waslaminated on both surfaces of the electromagnetic wave shield layer,substantially the same method was used.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 50 mm and a length of 200 mm. This was used as asample for evaluation.

[Materials]

(Electromagnetic Wave Shield Layer)

A PC film or a PET film produced as a mesh using each of variousconductive compounds and having a surface resistance value of 1[Ω/□] orless

(Conductive Compound Mesh)

-   -   AgC conductive printed mesh: Line: 100 μm; pitch: 500 μm;        surface resistance: 0.5Ω/□    -   Copper compound thin film mesh: Line: 10 μm; pitch: 300 μm;        surface resistance: 0.1Ω/□    -   Silver compound thin film mesh: Line: 10 μm; pitch: 180 μm;        surface resistance: 0.1Ω/□        (Base Substrate)    -   PC film: Polycarbonate film (thickness: 100 to 200 μm) produced        by MGC Filsheet Co., Ltd.    -   PET film: Easily adhesive polyethylene terephthalate (thickness:        200 μm) produced by Toyobo Co., Ltd.        (Protecting Layer)    -   PC sheet: Polycarbonate sheet (thickness: 1.5 mm to 20.0 mm)        produced by MGC Filsheet Co., Ltd.    -   PC film: Polycarbonate film (thickness: 100 μm) produced by MGC        Filsheet Co., Ltd.        (Method for Producing an Optically Transparent Electromagnetic        Wave Shield Laminate Using a Hotmelt-type Adhesive)

A hotmelt-type adhesive sheet was sandwiched between an electromagneticwave shield layer (PC film; thickness: 200 μm) and a protecting layer(PC sheet; thickness: 3.0 mm), and the assembly of layers was pressed at135° C. for 30 minutes.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 50 mm and a length of 200 mm. This was used as asample for evaluation.

[Hotmelt (HM)-type Adhesive]

-   -   Ethylene vinyl acetate (EVA)-based HM-type adhesive: Elphan        OH-501 produced by Nihon Matai, Co., Ltd.    -   Polyamide-based HM-type adhesive: Elphan NT-120 produced by        Nihon Matai, Co., Ltd.    -   Polyurethane-based HM-type adhesive: Kurangile S-1700 produced        by Kurabo Industries, Ltd.    -   Polyester-based HM-type adhesive: Kuranbetter G-6 produced by        Kurabo Industries, Ltd.    -   Polyolefin-based HM-type adhesive: Kuranbetter A-1510 produced        by Kurabo Industries, Ltd.        (Method for Producing an Optically Transparent Electromagnetic        Wave Shield Laminate Using a Pressure-sensitive Adhesive)

A pressure-sensitive adhesive sheet was sandwiched between anelectromagnetic wave shield layer (PC film; thickness: 200 μm) and aprotecting layer (PC sheet; thickness: 3.0 mm), and the assembly oflayers was pressed for 5 minutes.

Each of the resultant samples was kept still in a constant temperatureand humidity chamber (23° C., 50% RH) for 24 hours and then cut into apiece having a width of 25 mm and a length of 200 mm. This was used as asample for evaluation.

[Pressure-sensitive Adhesive]

-   -   Acrylic-based pressure-sensitive adhesive sheet: CS-9621        produced by Nitto Denko Corporation

Example 12

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

As a result of performing various evaluations, the following was found.In the “electromagnetic wave shield performance test” described above,the sample exhibited a good electromagnetic wave shield performance. Inthe “adhesive force test” described above, the sample had an adhesiveforce of 115 N. The “bendability test” described above was performedunder the conditions of a surface temperature (top) of 165° C., asurface temperature (bottom) of 165° C., a surface temperaturedifference of 0° C., and a radius of curvature of the die of 25 mm. As aresult, the external appearance was good, and the radius of curvature ofthe test piece was 25 mm.

Example 13

30.4% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.8% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, and4.0% by weight of photoinitiator were put into a container, and anadhesive composition was prepared in accordance with the “method forpreparing an adhesive” described above. The obtained adhesivecomposition was used for an electromagnetic wave shield layer of thecopper compound thin film mesh (PC film; thickness: 200 μm) and aprotecting layer (PC sheet; thickness: 3.0 mm) to produce a sample inaccordance with the “method for producing an optically transparentelectromagnetic wave shield laminate using an optically transparentadhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 70 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 14

32.1% by weight of urethane(meth)acrylate-based polymerizable oligomer,42.9% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 1.0% by weight of organophosphoruscompound, and 4.0% by weight of photoinitiator were put into acontainer, and an adhesive composition was prepared in accordance withthe “method for preparing an adhesive” described above. The obtainedadhesive composition was used for an electromagnetic wave shield layerof the copper compound thin film mesh (PC film; thickness: 200 μm) and aprotecting layer (PC sheet; thickness: 3.0 mm) to produce a sample inaccordance with the “method for producing an optically transparentelectromagnetic wave shield laminate using an optically transparentadhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 86 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 15

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 130° C., a surface temperature (bottom) of 130° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 29 mm.

Example 16

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 135° C., a surface temperature (bottom) of 135° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 27 mm.

Example 17

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 150° C., a surface temperature (bottom) of 150° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 18

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 19

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 180° C., a surface temperature (bottom) of 180° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 20

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 180° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 20° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 21

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 170° C., a surface temperature (bottom) of 160° C.,a surface temperature difference of 10° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 22

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 100 μm) and a protecting layer (PC film; thickness:100 μm) to produce a sample in accordance with the “method for producingan optically transparent electromagnetic wave shield laminate using anoptically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 96 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 23

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 10.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 110 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 50 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 51 mm.

Example 24

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 20.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 112 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 100 mm. As a result, the external appearance was good, andthe radius of curvature of the test piece was 105 mm.

Example 25

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 10 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 11 mm.

Example 26

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and protecting layers (PC sheet; thickness:1.5 mm each) provided above and below the copper compound thin film meshto produce a sample in accordance with the “method for producing anoptically transparent electromagnetic wave shield laminate using anoptically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 100 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 26 mm.

Example 27

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the silver compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 79 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Example 28

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the AgC conductive printed mesh (PCfilm; thickness: 200 μm) and a protecting layer (PC sheet; thickness:3.0 mm) to produce a sample in accordance with the “method for producingan optically transparent electromagnetic wave shield laminate using anoptically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 120 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, and theradius of curvature of the test piece was 25 mm.

Comparative Example 11

41.1% by weight of urethane(meth)acrylate-based polymerizable oligomer,54.9% by weight of (meth)acrylate-based polymerizable monomer, and 4.0%by weight of photoinitiator were put into a container, and an adhesivecomposition was prepared in accordance with the “method for preparing anadhesive” described above. The obtained adhesive composition was usedfor an electromagnetic wave shield layer of the copper compound thinfilm mesh (PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 1 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, peel-off occurred.

Comparative Example 12

An ethylene vinyl acetate (EVA)-based hotmelt-type adhesive wassandwiched between an electromagnetic wave shield layer of the coppercompound thin film mesh (PC film; thickness: 200 μm) and a protectinglayer (PC sheet; thickness: 3.0 mm) to produce a sample in accordancewith the “method for producing an optically transparent electromagneticwave shield laminate using a hotmelt-type adhesive” described above.Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 7 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer was air-bubbled, andpeel-off occurred.

Comparative Example 13

A polyamide-based hotmelt-type adhesive was sandwiched between anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a hotmelt-type adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 2 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, peel-off occurred.

Comparative Example 14

A polyurethane-based hotmelt-type adhesive was sandwiched between anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a hotmelt-type adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 92 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer was whitened and thevisibility was lost.

Comparative Example 15

A polyester-based hotmelt-type adhesive was sandwiched between anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a hotmelt-type adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 107 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer was foamed, andpeel-off occurred.

Comparative Example 16

A polyolefin-based hotmelt-type adhesive was sandwiched between anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a hotmelt-type adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 3 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, peel-off occurred.

Comparative Example 17

An acrylic-based pressure-sensitive adhesive sheet was sandwichedbetween an electromagnetic wave shield layer of the copper compound thinfilm mesh (PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using a pressure-sensitive adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 6 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 165° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer was foamed, andpeel-off occurred.

Comparative Example 18

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 125° C., a surface temperature (bottom) of 125° C.,a surface temperature difference of 0° C., and a radius of curvature ofthe die of 25 mm. As a result, the external appearance was good, but theradius of curvature of the test piece was 45 mm.

Comparative Example 19

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 190° C., a surface temperature (bottom) of 190° C.,a surface temperature difference of 25° C., and a radius of curvature ofthe die of 25 mm. As a result, the adhesive layer became wave-shaped,and the radius of curvature of the test piece was 25 mm.

Comparative Example 20

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 140° C.,a surface temperature difference of 25° C., and a radius of curvature ofthe die of 25 mm. As a result, the external shape was warped, and theradius of curvature of the test piece was 25 mm.

Comparative Example 21

30.0% by weight of urethane(meth)acrylate-based polymerizable oligomer,40.0% by weight of (meth)acrylate-based polymerizable monomer, 20.0% byweight of acrylamide derivative, 5.0% by weight of silane compound, 1.0%by weight of organophosphorus compound, and 4.0% by weight ofphotoinitiator were put into a container, and an adhesive compositionwas prepared in accordance with the “method for preparing an adhesive”described above. The obtained adhesive composition was used for anelectromagnetic wave shield layer of the copper compound thin film mesh(PC film; thickness: 200 μm) and a protecting layer (PC sheet;thickness: 3.0 mm) to produce a sample in accordance with the “methodfor producing an optically transparent electromagnetic wave shieldlaminate using an optically transparent adhesive” described above.

Various evaluations were performed in substantially the same manner asin Example 12. In the electromagnetic wave shield performance test, thesample exhibited a good electromagnetic wave shield performance. In theadhesive force test, the sample had an adhesive force of 115 N. Thebendability test was performed under the conditions of a surfacetemperature (top) of 165° C., a surface temperature (bottom) of 130° C.,a surface temperature difference of 35° C., and a radius of curvature ofthe die of 25 mm. As a result, the external shape was warped, andpeel-off occurred.

TABLE 3 Optically transparent electromagnetic wave shield laminatestructure (Meth)acrylate adhesive composition [% by weight] Film orsheet substrate Urethane (Meth)acryl- Acryla- Organo- (thickness[mm])Adhesive type (meth)acrylate ate poly- mide Silane phospho- Top pro-Bottom Conduc- Curing Main polymerizable merizable deriv- com- rusPhoto- tecting Shield protect- tive method component oligomer monomerative pound compound initiator layer layer ing layer compound Ex. 12Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copperadhesive based compound Ex. 13 Photocurable Acrylic- 30.4 40.6 20.0 5.04.0 PC(3.0) PC(0.2) Copper adhesive based compound Ex. 14 PhotocurableAcrylic- 32.1 42.9 20.0 1.0 4.0 PC(3.0) PC(0.2) Copper adhesive basedcompound Ex. 15 Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0)PC(0.2) Copper adhesive based compound Ex. 16 Photocurable Acrylic- 30.040.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copper adhesive based compound Ex.17 Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2)Copper adhesive based compound Ex. 18 Photocurable Acrylic- 30.0 40.020.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copper adhesive based compound Ex. 19Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copperadhesive based compound Ex. 20 Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(3.0) PC(0.2) Copper adhesive based compound Ex. 21Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copperadhesive based compound Ex. 22 Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(0.1) PC(0.2) Copper adhesive based compound Ex. 23Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0  PC(10.0) PC(0.2)Copper adhesive based compound Ex. 24 Photocurable Acrylic- 30.0 40.020.0 5.0 1.0 4.0  PC(20.0) PC(0.2) Copper adhesive based compound Ex. 25Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copperadhesive based compound Ex. 26 Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(1.5) PC(0.2) PC(1.5) Copper adhesive based compound Ex. 27Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Silveradhesive based compound Ex. 28 Photocurable Acrylic- 30.0 40.0 20.0 5.01.0 4.0 PC(3.0) PC(0.2) AgC paste adhesive based

TABLE 4 Optically transparent electromagnetic wave shield laminatestructure (Meth)acrylate adhesive composition [% by weight] Film orsheet substrate Urethane (Meth)acryl- Acryla- Organo- (thickness[mm])Adhesive type (meth)acrylate ate poly- mide Silane phospho- Top pro-Bottom Conduc- Curing Main polymerizable merizable deriv- com- rusPhoto- tecting Shield protect- tive method component oligomer monomerative pound compound initiator layer layer ing layer compound Com-Photocurable Acrylic- 41.1 54.9 4.0 PC(3.0) PC(0.2) Copper parativeadhesive based compound ex. 11 Com- Hot melt- EVA- PC(3.0) PC(0.2)Copper parative type based compound ex. 12 adhesive Com- Hot melt-Polyam- PC(3.0) PC(0.2) Copper parative type ide- compound ex. 13adhesive based Com- Hot melt- Polyure- PC(3.0) PC(0.2) Copper parativetype thane- compound ex. 14 adhesive based Com- Hot melt- Polyester-PC(3.0) PC(0.2) Copper parative type based compound ex. 15 adhesive Com-Hot melt- Polyolefin- PC(3.0) PC(0.2) Copper parative type basedcompound ex. 16 adhesive Com- Pressure- Acrylic- PC(3.0) PC(0.2) Copperparative sensitive based compound ex. 17 adhesive Com- PhotocurableAcrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copper parativeadhesive based compound ex. 18 Com- Photocurable Acrylic- 30.0 40.0 20.05.0 1.0 4.0 PC(3.0) PC(0.2) Copper parative adhesive based compound ex.19 Com- Photocurable Acrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2)Copper parative adhesive based compound ex. 20 Com- PhotocurableAcrylic- 30.0 40.0 20.0 5.0 1.0 4.0 PC(3.0) PC(0.2) Copper parativeadhesive based compound ex. 21

TABLE 5 Bending conditions Electromag- Adhesive Bendability testAdhesive type Heating temperature [° C.] netic wave force test Radius ofMain Bottom Surface Radius of shield per- T-peel curvature of Curingcompo- Top surface surface temperature curvature of formance teststrength test External test piece method nent temperature temperaturedifference die [mm] OK/Not OK [N/25 mm] appearance [mm] Ex. 12Photocurable Acrylic- 165 165 0 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 13Photocurable Acrylic- 165 165 0 25 ◯ 70 ◯ 25(◯) adhesive based Ex. 14Photocurable Acrylic- 165 165 0 25 ◯ 86 ◯ 25(◯) adhesive based Ex. 15Photocurable Acrylic- 130 130 0 25 ◯ 115 ◯ 29(Δ) adhesive based Ex. 16Photocurable Acrylic- 135 135 0 25 ◯ 115 ◯ 27(◯) adhesive based Ex. 17Photocurable Acrylic- 150 150 0 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 18Photocurable Acrylic- 165 165 0 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 19Photocurable Acrylic- 180 180 0 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 20Photocurable Acrylic- 180 160 20 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 21Photocurable Acrylic- 170 160 10 25 ◯ 115 ◯ 25(◯) adhesive based Ex. 22Photocurable Acrylic- 165 165 0 25 ◯ 96 ◯ 25(◯) adhesive based Ex. 23Photocurable Acrylic- 165 165 0 50 ◯ 110 ◯ 51(◯) adhesive based Ex. 24Photocurable Acrylic- 165 165 0 100 ◯ 112 ◯ 105(◯)  adhesive based Ex.25 Photocurable Acrylic- 165 165 0 10 ◯ 115 ◯ 11(◯) adhesive based Ex.26 Photocurable Acrylic- 165 165 0 25 ◯ 100 ◯ 26(◯) adhesive based Ex.27 Photocurable Acrylic- 165 165 0 25 ◯ 79 ◯ 25(◯) adhesive based Ex. 28Photocurable Acrylic- 165 165 0 25 ◯ 120 ◯ 25(◯) adhesive based

TABLE 6 Bending conditions Electromag- Adhesive Bendability test Heatingtemperature [° C.] netic wave force test Radius of Adhesive type BottomSurface Radius of shield per- T-peel curvature of Curing Main Topsurface surface temperature curvature of formance test strength testExternal test piece method component temperature temperature differencedie [mm] OK/Not OK [N/25 mm] appearance [mm] Com- Photocur- Acrylic- 165165 0 25 ◯ 1 X peeled Unmeas- parative able based off urable ex. 11adhesive (X) Com- Hot melt- EVA- 165 165 0 25 ◯ 7 X peeled Unmeas-parative type based off/ urable ex. 12 adhesive foamed (X) Com- Hotmelt- Polyam- 165 165 0 25 ◯ 2 X peeled Unmeas- parative type ide- offurable ex. 13 adhesive based (X) Com- Hot melt- Polyure- 165 165 0 25 ◯92 X 26(◯) parative type thane- whitened ex. 14 adhesive based Com- Hotmelt- Polyester- 165 165 0 25 ◯ 107 X peeled Unmeas- parative type basedoff/ urable ex. 15 adhesive foamed (X) Com- Hot melt- Polyolefin- 165165 0 25 ◯ 3 X peeled Unmeas- parative type based off urable ex. 16adhesive (X) Com- Pressure- Acrylic- 165 165 0 25 ◯ 6 X peeled Unmeas-parative sensitive based off/ urable ex. 17 adhesive foamed (X) Com-Photocur- Acrylic- 125 125 0 25 ◯ 115 ◯ 45(x) parative able based ex. 18adhesive Com- Photocur- Acrylic- 190 190 0 25 ◯ 115 X wave- 25(◯)parative able based shaped ex. 19 adhesive Com- Photocur- Acrylic- 165140 25 25 ◯ 115 X warped 25(◯) parative able based ex. 20 adhesive Com-Photocur- Acrylic- 165 130 35 25 ◯ 115 X warped/ Unmeas- parative ablebased peeled off urable ex. 21 adhesive (X)

The invention claimed is:
 1. A laminate manufactured by a methodcomprising the steps of: laminating two or more layers of polycarbonateresin film and/or sheet using a (meth)acrylate-based adhesivecomposition containing a (A) (meth)acrylate monomer, a (B)meth(acrylate) oligomer, an(C) acrylamide derivative, and a (D) silanecompound and/or an (E) organophosphorus compound to form a laminatehaving a thickness of 0.1 mm to 30 mm; heating the laminate at 130° C.to 185° C. so that a temperature difference between a top surface and abottom surface of the laminate is not more than 20° C.; and bending thelaminate after heating into a curved shape having a radius of curvatureof 10 mm or greater.
 2. The laminate of claim 1, which is usable for acover of an electronic device, a shield material for a housing, a coverfor a vehicle, a cover for a semiconductor production devices, or ashield material for a window material.
 3. The laminate of claim 1,wherein the step of heating the laminate is the step of heating thelaminate at 150° C. to 185° C.
 4. The laminate of claim 1, wherein oneof the two or more layers of polycarbonate resin film and/or sheet is anelectromagnetic wave shield layer, and at least one of the two or morelayers is a protecting layer.
 5. The laminate of claim 4, wherein theelectromagnetic wave shield layer contains a conductive compoundcontaining at least one metal component selected from the groupconsisting of silver, copper, aluminum, nickel, carbon, ITO (indiumoxide/tin oxide), ZnO, tin, zinc, titanium, tungsten and stainlesssteel.
 6. The laminate of claim 4, wherein the electromagnetic waveshield layer has an electromagnetic wave shield performance of 30decibels or greater.
 7. The laminate of claim 4, wherein theelectromagnetic wave shield layer contains at least one selected fromthe group consisting of a metal thin film mesh, a metal woven mesh, aconductive fiber mesh, and a conductive printed mesh.
 8. The laminate ofclaim 7, wherein the metal thin film mesh and the conductive printedmesh have a base substrate containing a polycarbonate resin, apolyethylene terephthalate resin, or a polyester resin.
 9. The laminateof claim 1, wherein the laminate has a 180 degree peel strength of 50N/25 mm width or greater.
 10. The laminate of claim 1, wherein thelaminate is not peeled or clouded after being treated for 200 hoursunder conditions of 65° C. and 95% relative humidity.
 11. The laminateof claim 1, wherein the (B) (meth)acrylate oligomer is at least one(meth)acrylate oligomer selected from the group consisting of urethane(meth)acrylate oligomer, polyester(meth)acrylate oligomer,epoxy(meth)acrylate oligomer, and polyol(meth)acrylate oligomer.
 12. Thelaminate of claim 11, wherein the urethane (meth)acrylate oligomer is analicyclic hydrocarbon compound.
 13. The laminate of claim 12, whereinthe urethane (meth)acrylate oligomer, which is the alicyclic hydrocarboncompound, is a compound derived from dicyclohexylmethaneisocyanate. 14.The laminate of claim 1, wherein the (C) acrylamide derivative is alkylacrylamide and/or alkyl methacrylamide.
 15. The laminate of claim 1,wherein the (C) acrylamide derivative is at least one selected from thegroup consisting of dimethyl acrylamide, isopropyl acrylamide, diethylacrylamide, and 4-acrylomorpholine.
 16. The laminate of claim 1, whereinthe (D) silane compound is at least one selected from the groupconsisting of amino-functional silane, epoxy-functional silane,vinyl-functional silane, mercapto-functional silane,methacrylate-functional silane, acrylamide-functional silane, andacrylate-functional silane.
 17. The laminate of claim 1, wherein the (D)silane compound is (3-(2,3-epoxypropoxy)propyl)trimethoxysilane.
 18. Thelaminate of claim 1, wherein the (E) organophosphorus compound is anacrylate phosphate compound.
 19. The laminate of claim 1, wherein themeth(acrylate)-based adhesive composition is a non-solvent(meth)acrylate-based adhesive composition.
 20. The laminate of claim 1,wherein the (meth)acrylate-based adhesive composition is a photocurable(meth)acrylate-based adhesive composition which is curable by visiblelight, an ultraviolet ray (UV) or an electron beam (EB).
 21. Thelaminate of claim 1, wherein the method comprises the step of forming acover film containing at least one selected from the group consisting ofan antioxidant, an ultraviolet absorber and a photostabilizer on one orboth of the surfaces of the laminate.
 22. The laminate of claim 21,wherein the cover film contains a thermosetting resin or a photocurableresin.
 23. The laminate of claim 21, wherein the cover film contains anacrylic-based resin compound or a silicone-based resin compound.
 24. Thelaminate of claim 1, wherein the layers containing the polycarbonateresin or the layers containing the (meth)acrylate-based adhesivecomposition contain at least one selected from the group consisting ofan antioxidant, an ultraviolet absorber and a photostabilizer.